WO2013192404A1

WO2013192404A1 - Polyheterosiloxane composition

Info

Publication number: WO2013192404A1
Application number: PCT/US2013/046784
Authority: WO
Inventors: David Deshazer; Martin Grasmann; Lizhi Liu; Nanguo Liu; Elizabeth Mcquiston; Shawn MEALEY; Randall Schmidt; Katherine Marie SHAHINIAN; Kwan SKINNER; Gang Lu; Jongwook CHOI
Original assignee: Dow Corning Corporation
Priority date: 2012-06-20
Filing date: 2013-06-20
Publication date: 2013-12-27
Also published as: WO2013192419A1

Abstract

A polyheterosiloxane composition includes (A) a first metal (M1), (B) a second metal (M2), and (C) siloxy units having the formula (R1 3SiO1/2), (R1 2SiO2/2), (R1SiO3/2), and/or (SiO4/2). Each R1 is independently a hydrocarbon or halogenated hydrocarbon group including 1 to 30 carbon atoms. The mole fractions of (A), (B), and (C) relative to each other is of the formula [(M1)]a[(M2)]b[R1 3SiO1/2]m[R1 2SiO2/2]d[R1SiO3/2]t[SiO4/2]q, wherein a and b are each independently from 0.001 to 0.9, m, d, t, and q are each independently from zero to 0.9, m, d, t, and q cannot all be zero, and the sum of a+b+m+d+t+q ≈ 1. At least one oxygen atom of the siloxy units is bonded to at least one of (M1) and/or (M2). The composition exhibits a quantum yield of at least 0.05% and at least one of (M1) and (M2) is a lanthanide metal.

Description

POLYHETEROSILOXANE COMPOSITION

[0001] Incorporation of various metals into polysiloxanes to form polyheterosiloxanes is of great interest for a wide range of applications. Lanthanide metals luminesce due to their electronic structures. However, the use of lanthanides metals in luminescent materials is limited by standard energetic high temperature synthesis and blending and also by quenching of luminescence at high lanthanide concentration. Quenching can occur above a threshold lanthanide concentration where lanthanide metal ions are allowed to aggregate and subsequent coordinate changes in the electronic structure can lead to non-radiative routes to ground including cross relaxation. In some cases, excited state absorption can lead to quenching. Undetermined mechanisms, typically described as concentration quenching, may also occur. The threshold concentration for quenching can be as low as 1%, limiting the brightness of luminescent materials. In addition, other issues may also arise relative to incorporation of metals into polysiloxanes. Accordingly, there remains an opportunity to develop improved materials.

SUMMARY OF THE DISCLOSURE

[0002] In one embodiment, this disclosure provides a polyheterosiloxane composition including (A) a first metal (Ml), (B) a second metal (M2), and (C) siloxy units having the formula (R^SiOm), (R^SiO^), (R¹Si0_{3 2}), and/or (Si0_{4 2}). Each R¹ is independently a hydrocarbon or halogenated hydrocarbon group including 1 to 30 carbon atoms. The mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹ ₃Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si0_3/2]_t[Si0_4/2]_q, wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9, m, d, t, and q cannot all be zero, and wherein the sum of a+b+m+d+t+q ~ 1. At least one oxygen atom of the siloxy units is bonded to at least one of (Ml) and/or (M2). The composition exhibits a quantum yield of at least 0.05% and at least one of (Ml) and (M2) is a lanthanide metal.

[0003] In another embodiment, this disclosure provides a method of forming the polyheterosiloxane composition. The method includes the step of reacting (Α') a metal (M3) alkoxide, (Β') an optional hydrolyzable metal (M4) salt, (C) a silicon- containing material having silicon-bonded hydroxy groups, and (D) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β'). At least one of (M3) and (M4) is a lanthanide metal.

[0004] In still another embodiment, this disclosure provides a sensitized polyheterosiloxane including (A), (B), and (C). In this embodiment, the sensitized polyheterosiloxane composition also includes a photosensitizer present in an amount of less than 3 moles of photosensitizer per one mole of the lanthanide metal. In various embodiments, the photosensitizer imparts a larger peak emission intensity to the sensitized polyheterosiloxane composition at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, or 320 to 480 nm as compared to a control polyheterosiloxane composition free of the photosensitizer.

[0005] In a further embodiment, this disclosure also provides a method of forming the sensitized polyheterosiloxane composition. The method includes the step of reacting (Α'), (Β'), (C), and (E) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β') to form a polyheterosiloxane composition. The method also includes the step of (II) introducing the photosensitizer to one or more of (Α'), (Β'), (C), and (E) prior to the step of reacting and/or the step of introducing the photosensitizer to the polyheterosiloxane composition, to form the sensitized polyheterosiloxane composition.

[0001] In still another embodiment, this disclosure provides a silicone composition that includes the (I) polyheterosiloxane composition and (II) a curable silicone. This disclosure also provides a cured product of the silicone composition and an article that includes a substrate and a coating disposed on the substrate, wherein the coating includes the cured product of the silicone composition.

BRIEF DESCRIPTION OF THE FIGURES

[0006] Figure 1 is an excitation and emission photoluminescence spectra of Example 26 at 10 wt % in toluene obtained using a Jobin-Yvon SPEX Fluorolog2 device with a 450W xenon lamp and 495 nm absorption filter. The excitation spectrum intensity is normalized to the peak height at approximately 395 nm, and is collected while monitoring the emission at 615 nm. The emission spectrum intensity is normalized to the peak height at 615 nm, and is collected while illuminating the sample with an excitation wavelength of 395 nm. [0007] Figure 2 is a TEM of Tio.eoEuo.cBD™ 0.27T 0.1 of Example 1.

[0008] Figure 3 is a line graph illustrating excitation and emission spectra of

Examples 1, 39 and 4 that include Eu, Tb and Dy, respectively.

[0009] Figure 4A is a graph of excitation intensity as a function of wavelength of Examples 63 and 64 wherein emission is monitored at about 614 nm.

[0010] Figure 4B is the graph of Figure 1A corrected for detector saturation having a different scale of the Y axis.

[0011] Figure 4C is also the graph of Figure 1A corrected for detector saturation having a different scale of the Y axis.

[0012] Figure 5A is a graph of excitation intensity as a function of wavelength of Examples 65 and 66 wherein emission is monitored at about 614 nm.

[0013] Figure 5B is the graph of Figure 2A corrected for detector saturation having a different scale of the Y axis.

[0014] Figure 5C is also the graph of Figure 2A corrected for detector saturation having a different scale of the Y axis.

[0015] Figure 6A is a graph of excitation intensity as a function of wavelength of Examples 67, 68 and 69 wherein emission is monitored at about 614 nm.

[0016] Figure 6B is the graph of Figure 3A corrected for detector saturation having a different scale of the Y axis.

[0017] Figure 6C is also the graph of Figure 3A corrected for detector saturation having a different scale of the Y axis.

[0018] Figure 7 is a graph of excitation intensity as a function of wavelength of Examples 67-71 wherein emission is monitored at about 614 nm.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0019] This disclosure describes a polyheterosiloxane composition (hereinafter described as the "composition") that includes (A) a first metal (Ml), (B) a second metal (M2), and (C) siloxy units having the formula (R^SiOm), (R^SiC^a), (R¹Si032), and/or (S1O₄2). This disclosure also describes a silicone composition that includes the (I) polyheterosiloxane composition and a (II) curable silicone (i.e., a curable silicone composition different from the silicone composition introduced immediately above). This disclosure also described a sensitized polyheterosiloxane composition that includes a photosensitizer, as described in greater detail below. [0020] The physical properties of the polyheterosiloxane composition, as described, (e.g. emission, excitation, lifetimes, quantum yields, etc.) may also be descriptive of the physical properties of the silicone composition as a whole.

[0021] The composition may include one (A) first metal (Ml), two first metals (Ml), or a plurality of first metals (Ml). The first metal (Ml) is not particularly limited and may be a lanthanide metal or a non-lanthanide metal. (Ml) may be chosen from Ti, Zr, Al, and Zn, or Ti, Zr, and Al, or Ti, Al, Ge, Zr, Hf, Mn, Nb, Y, Ta, and V, or Ti, Zr, Al, Zn, Hf, Ta, Y, and Nb, or Ti, Zr, Al, Ge, Ta, Nb, and Sn, or La, Pr, Sm, Gd, Tb, Dy, Ho, Tm, and Lu, or Gd, Tb, Dy, Ho, Tm, and Lu, or Eu, Yb, Er, Nd, Dy, Sm, and Tb, and/or any single metals or combinations thereof. In various additional embodiments, (Ml) is chosen from Sn, Cr, Ba, Sb, Cu, Ga, In, Mg, Mo, Te, W, Sr, and/or any single metals or combinations thereof. The oxidation state of (Ml) is typically independently from 1 to 5, 1 to 4, 1 to 2, 2 to 3, 2 to 4, or any range or combination of ranges or values therebetween. If more than one (A) first metal (Ml) is utilized, then each (Ml) may independently have the same or different oxidation states.

[0022] The composition may include one (B) second metal (M2), two second metals (M2), or a plurality of second metals (M2). The second metal (M2) is not limited. In one embodiment, at least one of (Ml) and (M2) is or includes a lanthanide metal. (M2) may be one or more of those metals described above or may be any other metal in the periodic table. (M2) may be a lanthanide metal or a non-lanthanide metal. In another embodiment, one of (Ml) and (M2) is a lanthanide metal and the other of (Ml) and (M2) is a non-lanthanide metal chosen from aluminum (Al), zirconium (Zr), and combinations thereof. For example, in this embodiment, (Ml) or (M2) may be any one or more lanthanide metals, including combinations thereof, or may be Al, Zr, or combinations thereof.

[0023] For example, (Ml) and (M2) may be one of the following:

or more Non-Lanthanide Metals one or more Non-Lanthanide Metals

Lanthanide Metal Lanthanide Metal

Lanthanide Metal Aluminum

Lanthanide Metal Zirconium

Combination of Aluminum and

Lanthanide Metal

Zirconium

Aluminum Lanthanide Metal

Zirconium Lanthanide Metal

Combination of Aluminum and

Lanthanide Metal

Zirconium

[0024] Each of (Ml) and/or (M2) may independently include one or more lanthanide and/or non-lanthanide metals, singly or in combination. More than one lanthanide metal may be utilized. A mixture of non-lanthanide metals may be utilized along with one or more lanthanide metals. (Ml) and/or (M2) may each independently be any described above and/or include or be a combination of Eu and Y, Eu and La, Eu and Ce, Eu and Gd, Eu and Tb, Eu and Dy, Eu and Sm, Ce and Tb, Tb and Yb, Er and Yb, Pr and Yb, Tm and Yb, and/or combinations thereof. One or more of Ml and M2 may be Eu³⁺. For example, the composition may include Eu³⁺ and exhibit excitation and emission transitions between the ⁵D and ⁷F energy levels in the 4f orbital. A principal excitation line may be observed at approximately 395 nm and principal emission line may be observed at approximately 615 nm. Alternatively, (M2) may be chosen from Ce, Eu, Nd, Er, Sm, Dy, Tb, and/or combinations thereof, or chosen from Eu, Er, Tb, Nd, and combinations thereof.

[0025] The composition also includes (C) siloxy units having the formula (R^SiOm), (R^SiO^), (R¹Si0_{3 2}), and/or (Si0_{4 2}). These units may be alternatively described as organopolysiloxane segments and are known in the art as M, D, T, and Q units, respectively. The composition may include one or more M, D, T, and/or Q units, e.g. "M" and "D" units, "M" and "T" units, "M" and "Q" units, "D" and "T" units, "D" and "Q" units, or "T" and "Q" units, and/or combinations thereof.

[0026] Each R¹ is typically independently a hydrocarbon or halogenated hydrocarbon group including 1 to 30, 1 to 20, 1 to 15, 1 to 12, 1 to 10, 1 to 5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, carbon atoms, or any value or range of values therebetween. Any R¹ may be the same or different from any other R¹. Non- limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, octadecyl, cyclohexyl, aryl, phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl, halogenated hydrocarbon, 3,3,3- trifluoropropyl, 3-chloropropyl, and dichlorophenyl, groups. At least one of R¹ may be phenyl. The number of siloxy units may vary. The number and type of siloxy units may affect the molecular weight of the organopolysiloxane segment, and hence the molecular weight of the composition.

[0027] The (C) siloxy units may include greater than 50 mole or weight percent of R¹Si0₃ 2 siloxy units where R¹ is phenyl; R^SiO^ siloxy units where one R¹ substituent is phenyl, and the other R¹ substituent is methyl; or R¹ ₂Si0₂2 and R¹Si0_{3 2} siloxy units where one R¹ substituent in the R^SiO^ siloxy unit is phenyl, and the other R¹ substituent is methyl, and where R¹ is phenyl in the R¹Si0_{3 2} siloxy unit. One or more siloxy units may have the formula [(C6Hs)SiC>3_/2]_d, [(C₆H5)₂Si0_2/2]_d[(C₆H5)Si03/₂]t, or [(CH3)(C₆H₅)Si0_2/2]_d [(C₆H₅)Si03/₂]t.

[0028] The composition may include at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or at least 98 or 99,%, or any value or range of values therebetween, of (A), (B), and (C) based on a total weight of the composition. Alternatively, the composition may include approximately 100% of (A), (B), and (C) based on a total weight of the composition. Any range of values including those above, or any one or more values between those above, may also be utilized. Any remaining percent by weight of the composition may include one or more solvents, one or more counterions, e.g. benzoates, naphtoates, and acetates, and/or one or more components used to form the composition.

[0029] The varied amounts of each of (A), (B), and (C) are typically described relative to mole fractions of each to a total number of moles of (A), (B), and (C). For example, the mole fractions of (A), (B), and (C) in the polyheterosiloxane composition relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹3Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si03/₂]t[Si0₄/₂]_q. The subscript m denotes the mole fraction of the optional "M" unit (R^SiOi^). The subscript d denotes the mole fraction of the optional "D" unit (R^SiO^). The subscript t denotes the mole fraction of the optional "T" unit (R¹Si0_3/2). The subscript q denotes the mole fraction of the optional "Q" unit (Si0_{4 2}).

[0030] a and/or b is each typically independently from 0.001 to 0.9, 0.010 to 0.9, 0.001 to 0.7, 0.1 to 0.7, 0.1 to 0.6, 0.2 to 0.5, 0.2 to 0.8, 0.3 to 0.7, 0.4 to 0.6, or about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, or any value or range of values therebetween. Alternatively, a and/or b may be each independently from 0.001 to 0.9, 0.001 to 0.5, 0.01 to 0.3, or 0.05 to 0.25. For example, when (Ml) is a non-lanthanide metal and (M2) is a lanthanide metal, a may be from 0.1 to 0.9 and b may be from 0.001 to 0.5. The total metal content of the composition, i.e., the sum of a+b, may be from 0.1 to 0.9, from 0.2 to 0.8, from 0.3 to 0.7, from 0.4 to 0.6, about 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, mole fraction, or any value or range of values therebetween.

[0031] m is typically from zero to 0.9, 0.1 to 0.6, or 0.2 to 0.5 or any value or range of values therebetween, d is typically from zero to 0.9, 0.1 to 0.5, or 0.1 to 0.3 or any value or range of values therebetween. Each of t and q is typically independently from zero to 0.9, 0.010 to 0.9, 0.001 to 0.7, 0.1 to 0.7, 0.1 to 0.6, or 0.2 to 0.5 or any value or range of values therebetween. Moreover, m, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1. The terminology "~" describes that the sum of a, b, m, d, t, and q is approximately equal to 1. The sum may be 0.99, 0.98, 0.97, 0.96, 0.95, etc, or any value or range of values therebetween. If the sum does not equal 1, then the composition may include residual amounts of groups that are not described by the aforementioned formula. The composition may include up to about 5 mole percent of other units, such as those that include Si-OH bonds.

[0032] The composition may have a formula [(Ml)]_a[(M2)]_b[R¹ ₃SiOi/2]_m[R¹2Si0₂/2]ci [R¹Si0₃/2]t[Si0₄/2]q, wherein Ml is a combination of metals, e.g. Ti and Zn, a is 0.12, b is 0.08, m is zero, d is 0.6, t is 0.2, and q is zero. Alternatively, Ml may be a single metal, e.g. Ti, wherein a is 0.6, b is 0.05, m is zero, d is 0.2675, and T is 0.0825, or, e.g. Ti, wherein a is 0.5, b is 0.2, m is zero, d is 0.225, t is 0.075, and q is zero. The composition may have one of the following formulas, Tio.1Zno.02Euo.08Do.6T0 2; Ti0.6Eu0.05D0.2675 0.0s25; i0.5Eu0.2D0.225 0.075; or Ti₀.₄Euo.₄Do.i₅To.o5- Therein, a may be from 0.1 to 0.8, b may be from 0.05 to 0.5, c may be from zero to 0.8, d may be from zero to 0.8, with the provisos that c and d both cannot be zero and the sum of a+b+c+d ~ 1, and wherein at least one of (Ml) and (M2) is a lanthanide metal.

[0033] The number of moles of each component of the composition may be determined using common analytical techniques. The number of moles of the siloxy units may be determined by ²⁹Si liquid or solid state NMR, ⁴⁸Ti NMR, ²⁷ Al NMR, FT- IR, TEM EDX, ICP, XRF, GCMS, GC functionality, ICP, etc. Alternatively, the number of moles of each component may be calculated from the amounts of each used in the process to prepare the composition, and accounting for any losses (such as removal of volatile species) that may occur.

[0034] The composition may also include from 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, from 1 to 15, from 1 to 10, or from 1 to 5, or any value or range of values therebetween, percent by weight, alkoxy groups. Residual alkoxide (-OR) groups may also be present in polyheterosiloxane structures and may be bonded to (Ml) and Si, as determined using ²⁹Si and ¹³C NMR, e.g. in an organic solvent. Residual counter ions from metal salts may also be present and may be bonded or chelated to (Ml) and (M2).

[0035] One or more atoms of (Ml) and (M2) may be bonded to the same or different silicon atoms, e.g. through an oxygen bond. At least one oxygen atom of the siloxy units is bonded to at least one of (Ml) and/or (M2) and/or one or more (C) siloxy units. Two or more oxygen atoms of one or more siloxy units may be bonded to (Ml) or (M2) or to both (Ml) and (M2). Atoms of (Ml) may be bonded to other atoms of (Ml) or (M2). For example, atoms of (Ml) may be linked via oxygen atoms to atoms of (Ml) and/or (M2), e.g. M1-0-M1-0-M2 or M1-0-M2. Atoms of (Ml) may also have a one or more substituents bonded thereto such as residual or un-reacted substituents used to form the composition.

[0036] Atoms of (M2) may be bonded to other atoms of (M2), (Ml), and/or one or more (C) siloxy units. Atoms of (M2) may be linked via oxygen atoms to atoms of (M2) and/or (Ml), e.g. M2-0-M2-0-M1 or M2-0-M1. Atoms of (M2) may also have a one or more substituents bonded thereto such as residual or un-reacted substituents used to form the composition.

[0037] The composition may include various heterosiloxane structures including, but not limited to, structures having Si-O-Si, Si-O-Ml, Ml-O-Ml, and M1-0-M2 bonds as well as Si-0-M2 and M2-0-M2 bonds. Typically, a concentration of metal to metal bonds (e.g. Ml-O-Ml, M1-0-M2, M2-0-M2) is controlled so as to minimize formation of metal aggregates or particles of sufficient size to either render the composition insoluble in organic solvents or are of insufficient size to be detected using TEM techniques.

[0038] The composition may have "metal-rich" domains and "siloxane-rich" domains. As used herein the terminology "metal -rich" domains describes structural segments wherein a plurality of bonds include (Ml) or (M2) (i.e., Ml-O-Ml, Ml-O- M2, M2-0-M2, Ml-O-Si, or M2-0-Si). As used herein, the terminology "siloxane- rich" describes structural segments wherein a plurality of bonds are siloxane (Si-O-Si) bonds. The "metal-rich" domains may be present such that the amount of metal to metal bonds (Ml-O-Ml, M1-0-M2, M2-0-M2) is minimized so as to minimize formation of metal aggregates or particles of sufficient size to minimize their solubility in hydrocarbons. The composition may also include -(Si-0-Ml-0-M2)- bonds. In one embodiment, Ti and/or Al can act as a bridge to Ml to bridge siloxy units with lanthanide-oxygen units. Use of ¹⁷0 NMR, ⁴⁸Ti NMR and/or ²⁷ Al NMR may increase resolution or ability to quantify Si-0 and Lanthanide-0 bonds.

[0039] Alternatively, the metal rich domains may not be of sufficient size to be observed using high resolution transmission electron micrographs (TEM). Thus, the (Ml) and (M2) metals may be sufficiently distributed in the composition and have a domain size smaller than 10 nanometers, alternatively smaller than 5 nanometers, or alternatively smaller than 2 nanometers (detection limits for the TEM). Alternatively, NMR, FT-IR, and/or X-Ray PDF techniques may be utilized throughout this disclosure to determine bonding, composition, etc.

[0040] The composition is typically soluble in an hydrocarbon solvent, such as an aromatic hydrocarbon solvent, and may be soluble in other organic solvents as well. As used herein, "soluble" describes that the composition dissolves in, for example toluene, to form a homogeneous solution having a concentration of at least 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or about 100, weight percent of the composition in toluene at 23°C. The composition may also be soluble in other organic solvents, such as chloroform, carbon tetrachloride, THF, and butyl acetate.

[0041] The composition typically has a weight average molecular weight (M_w) from 1,000 to 1,000,000, from 2,000 to 400,000, from 2,000 to 200,000, from 5,000 to 750,000, from 10,000 to 500,000, from 20,000 to 350,000, from 30,000 to 300,000, from 40,000 to 250,000, from 50,000 to 200,000, from 60,000 to 175,000, from 70,000 to 150,000, from 80,000 to 140,000, from 90,000 to 130,000, from 100,000 to 1250,000, g/mol, or any value or range of values therebetween. The molecular weight may be determined using modified GPC techniques to minimize possible interactions between the sample and the column system. For example, the molecular weight may be determined by GPC analysis using triple detectors (light scattering, refractometer, and viscometer) with a column (PL 5u 100a 100 x 7.8mm) designed for rapid analysis or Flow Injection Polymer Analysis (FIPA).

[0042] The composition is photoluminescent and may emit visible or ultraviolet light when exposed to, or excited by, visible or ultraviolet light. The composition typically exhibits a quantum yield of at least 0.05%, as determined using the formula described in greater detail below. In various embodiments, the composition exhibits a quantum yield of at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, %, or even greater, of from 5 to 75, 10 to 70, 15 to 65, 20 to 60, 25 to 55, 30 to 50, 35 to 45, 40 to 60, 40 to 50, 45 to 55, or 50 to 60, %, or any value or range of values therebetween. It is contemplated that any of the aforementioned values may be a minimum or a maximum for a range of quantum yield for the composition and all combinations of the aforementioned values are hereby expressly contemplated. The composition may alternatively exhibit a quantum yield of 0.5, 1, 5, or 10% or any value or range of values set forth above or between those values set forth above. In various compositions, e.g. EuTiZnSi, quantum yields may be from 35 to 55% measured, for example, using an integrating sphere attached to a Flurolog-3 fluorescence spectrometer. In other compositions, e.g. ZrTbSi, quantum yields may be from 5.9% to 7.4%. The quantum yield may be alternatively described as any value, or range of values, both whole and fractional, within or between any one or more values described above. In various embodiments, the aforementioned quantum yield may vary by ±1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, %.

[0043] A limited size of the metal rich domains may lead to enhanced photoluminescence. For example, concentrations of lanthanide ions may exceed conventional concentration quenching thresholds without reduction in quantum yield. Photoluminescence may be assessed by measuring the absorption spectrum, the photoluminescent emission (PL) spectrum, or the photoluminescent excitation (PLE) spectrum of the composition. The absorption spectrum may be measured with standard spectrometers such as a Varian Carry 5000 spectrophotometer (Agilent Technologies, Palo Alto, CA, USA). The PL excitation and emission spectra may be measured using a spectrofluorometer. A representative spectrofluorometer is the Fluorolog-2 or -3 spectrofluorometer (FL2 or FL3) (HORIBA Jobin-Yvon Inc. Edison, NJ, USA). [0044] The efficiency in which a photoluminescent material converts light from one wavelength to another can be described as quantum yield (QY). Alternatively, Quantum Yield can be described as a percentage of overall light conversion (photons absorbed to photons emitted) of a material. While it is possible to determine the QY of a material by comparing the absorption, PL and PLE spectra of a test composition to a reference composition, the QY may be measured more directly using a spectrometer coupled integration sphere, where the absorption and PL spectra of a composition are referenced against a blank reference sample. Representative equipment is an Ocean Optics USB4000 spectrometer fiber-optically coupled to an approximately 4 cm integration sphere, illuminated by a light emitting diode (LED) and run by Ocean Optics' Spectra Suite software (Ocean Optics, Dunedin, FL, USA). Alternatively, equipment such as Fluorolog-2 or -3 spectrofluorometers (FL2 or FL3) (HORIBA Jobin-Yvon Inc. Edison, NJ, USA) may be utilized with appropriate accessories. For example, a combination of a UV-Vis spectrum and a PL/PLE spectra may be utilized.

[0045] In various embodiments, the absorption and emission of a sample are measured under the illumination of an LED with a center wavelength of 395 nm. The test sample is typically placed in the approximately 4 cm integration sphere in a glass vial with an absorption cut-off less than 350 nm. Incident light is typically measured by integrating the photon count in the range 350-450 nm, and emitted light in the range 480-850 nm. A different LED light source and/or photoluminescent material may require changing the integration ranges.

[0046] The composition may emit visible and infrared light having a wavelength in the range of 400 to 1700 nm when excited by light having a wavelength of 200 to 1000 nm, where the emitted light is a longer wavelength than the excitation wavelength, with a photon quantum yield efficiency of at least 0.1%, where photon quantum yield is determined using the equation described above. Alternatively, the composition may emit visible light having a wavelength of 580 to 750 nm when excited by light having a wavelength of 250 to 550 nm. Alternatively, the composition may emit visible light having a wavelength of 610 to 620 nm when excited by ultraviolet light having a wavelength of 390 to 400 nm. The quantum yield may be at least 1%, alternatively 2%, alternatively 5%, alternatively 10%, alternatively 20%, alternatively 30%, alternatively 40%, alternatively 50%, or alternatively 60%. [0047] The composition may alternatively emit visible light when excited by a UV light source. The emitted light may have a wavelength ranging from 450 to 750 nm while the excitation light source may have a wavelength ranging from 250 to 520 nm. The composition may alternatively emit visible light having a wavelength of 450 to 650 nm when excited by UV light. The composition alternatively may emit infrared light having a wavelength of 1450 to 1650 nm when excited by a light source having a wavelength from 650 to 5,000 nm. Alternatively, the composition may emit near IR light having a wavelength of 1000 to 1100 nm when excited by a light source having a wavelength from 650 to 5,000 nm. The composition may alternatively emit light having a wavelength of 400 to 1700 nm when excited by a light source having a wavelength of 200 to 1000 nm. Typically, the emitted light has a longer wavelength than the excitation light source. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0048] The human eye tends to be most sensitive at wavelengths of light from 450 to 650 nm. Typically, light having wavelengths above and below this range is of lesser value for lighting applications. In addition, when a full range of wavelengths is not present, lighting quality and color quality tends to be reduced. Narrow band red emission at approximately 615 nm balances strong red emission for suitable color rendering with visually bright emission. For example, compositions that include Si+Eu³⁺ resin phosphors tend to exhibit a CIE color value of x=0.66, y=0.34, a nearly saturated red, while the emitting in a visually bright range. However, for a similar color value, the peak tends to be approximately 650 nm because much of the broadband emission is over 700 nm, and lost, reducing brightness and system efficacy. The CIE color values of the emitted light may be as follows: x from 0.62 to 0.68, from 0.64 to 0.67, or from 0.65 to 0.66, and y from -.31 to 0.37, from 0.32 to 0.36, or from 0.33 to 0.34.

[0049] The 1931 CIE (International Commission on Illumination) color space is defined by tristimulus values, X, Y and Z. In this model, Y represents luminance, Z corresponds to the human eye's blue response, and X is a mix of color responses and orthogonal to Y. They are calculated according to the formulas: X = \ ΐ(λ )χ^, (λ )άλ

o

Y = \ ι(λ )γ (λ )άλ

ο

Ζ = ΐ(λ )ζ' (λ )άλ

0

wherein χ'(λ), γ'(λ) and

are color matching functions with peaks at approximately 450 nm, 550 nm and 600 nm respectively, and Ι(λ) is the spectra power distribution. The reported color or chromaticity coordinates x, y and z are calculated x=X/(X+Y+Z), y=Y/(X+Y+Z), and z=Z/(X+Y+Z) and by inspection x+y+z=l.

[0050] Steady state emission and excitation measurements are typically collected using a Horiba Jobin- Yvon Fluorolog 3 spectrofluorometer with three slit double grating excitation and emission monochromators and with dispersions of 2.1 nm/mm (1200 grooves/mm). The spectra are obtained with a 450 W xenon continuous wave lamp and detected at an angle of 90 degrees to the excitation source for solutions in 1 cm quartz cuvettes and at 30 degrees for measurements of powders in the solid state or thin films via a photomultiplier tube detector. Measured films are typically discs 3 mm thick with 5% wt Si+Ln resins in varying silicone hosts. Samples in solution are typically measured for concentrations between 1.5% and 5% to yield optical densities below 0.10. Measurement procedures and references follow from Mavrodineau, Schultz and Menis 'Accuracy in Spectrophotometry and Luminescence Measurements' , NBS Special Publications p. 378 (1973), and were updated as needed in compliance with the user manuals of cited instrumentation. In the measurement, the background thermal noise (or the dark offset) is corrected all the time. There is also a reference photodiode to collect the variations of intensities in the excitation source (Rc). An intensity standard reference material (2940-C from NIST) is used to monitor variations in the photomultiplier tube detector (PMT) signal (Rs). Then the excitation/emission spectra are typically reference corrected for both variations in intensities in the excitation source and variations in the photomultiplier tube detector by utilizing the ratio of PMT spectral response to Rc and Rs. Luminescent quantum yields are typically measured with a six (6) inch integrating sphere accessory attached via optical fibers to the spectrofluorometer. These data are typically collected in two steps, wherein a first step includes measuring the absorption of a blank reference material in the integrating sphere while avoiding saturation of the detector by using the appropriate neutral density filters for the selected bandpass. The bandpass for these measurements is typically set between 1.5 and 2 nm, and the range scanned includes both the excitation source and the emission of the material. The second step typically includes replacing the blank reference with the sample while the measurement is repeated. These datasets are then typically analyzed in the vendor provided software, where the difference in the emission and the excitation is used to produce the resulting quantum yield for the material.

[0051] Absorption spectra are typically determined by monitoring the strongest absorption peak of the composition, e.g. Si+Eu³⁺ luminescent silicones via population of the ⁵L₆ level at 393.5 nm, and collecting data via the optically dilute method. Optical densities are typically less than 0.1 and are typically collected on a UV-Vis in 10 mm quartz cuvettes. Data is typically obtained for three different concentrations, e.g. 4 wt , 3.2 wt% and 2.5 wt , with targeted absorptions, e.g. of 0.100, 0.081 and 0.060. However, the concentrations may be from 1.5 to 8.0 wt , depending on the total metal content of the composition.

[0052] In one method, combined absorption and fluorescence data are used to calculate quantum yields relative to a standard reference. Because the optical densities can be kept below < 0.1, quantum yields could be determined via the following equation:

wherein QY is the quantum yield of the sample, QY_r is the quantum yield of the reference, A is the absorbance at the excitation wavelength λ, n is the refractive index, and D is the integrated emission intensity. The subscripts r and x indicate a reference value and an experimental value, respectively. For example, quinine sulfate in 1.0 N sulfuric acid can be used as a reference with an excitation at 340 nm and will produce emission between 370 nm and 660 nm. This solution has an established quantum yield of 0.546. Other references include fluorescein (470 nm excitation, 480-700 nm emission, QY 0.91) and rhodamine (535 nm excitation, 550 - 750 nm emission, QY 1.00). These reference materials are all commonly used and referenced in the literature, e.g. in Eaton, D., International Union of Pure and Applied Chemistry Organic Chemistry Division Commission on Photochemistry; and/or the Journal of photochemistry and photobiology. B, Biology, 1988. 2(4): p. 523, each of which are expressly incorporated herein by reference relative to these particular materials.

[0053] The composition may also have an asymmetry ratio, typically in an embodiment utilizing Eu³⁺, of from 3.0 to 6.0, from 3.1 to 5.9, from 3.2 to 5.8, from 3.3 to 5.7, from 3.4 to 5.6, from 3.5 to 5.5, from 3.6 to 5.4, from 3.7 to 5.3, from 3.8 to 5.2, from 3.9 to 5.1, from 4.0 to 5.0, from 4.1 to 4.9, from 4.2 to 4.8, from 4.3 to 4.7, from 4.4 to 4.6, or 4.5, or any value or range of values therebetween, as determined using a Flurolog3 (Horiba Scientific) spectrofluorometer by measuring the ratio of the peak emission value of the ⁵Do→ ⁷F₂ transition at 614 nm to the ⁵Do→ ⁷Fi transition at 590 nm. The asymmetry ratio can be calculated according to the method described below. In addition, the asymmetry ratio may change based on selection of lanthanide metal, as can be calculated by those known in the art.

[0054] Asymmetry ratios can be calculated by measuring a ratio of a peak emission value of the composition, e.g. of the ⁵Do→ ⁷F₂ transition at 614 nm to the ⁵Do→ ⁷Fi transition at 590 nm, which correspond to electric and magnetic dipoles, respectively. In one embodiment, the ¾o→ ⁷F₂ transition is a "hypersensitive" electric dipole, and is very sensitive to the local electric field surrounding a lanthanide ion, e.g. Eu³⁺ ion. The ⁵Do→ ⁷Fi transition is a magnetic dipole, however, and tends to not be sensitive to the local Eu³⁺ environment. Asymmetry ratios close to or less than 1 tend to indicate that only a small amount of distortion takes place near the lanthanide ion, e.g. Eu³⁺, center and that the ion is near an inversion center/resides in a high symmetry environment, while values greater than 1 denote Eu³⁺ in a low symmetry environment. This rationale and explanation may also apply to other lanthanide metals as well.

[0055] The composition may also have a radiative lifetime calculated using emission spectra generated using a fluorescence spectrometer and a 393.5nm excitation wavelength. The terminology "radiative lifetime" describes the lifetime of a material in the absence of any non-radiative processes involved in the conversion of light. Radiative lifetime values for the composition, e.g. a EuTiZnSi composition, may be from 2.43 to 2.73 using a Flurolog-3 fluorescence spectrometer and a photo- multiplier tube detector. Radiative lifetime measurements may be calculated according to the method described below.

[0056] Radiative lifetimes can be calculated from a corrected emission spectrum of a composition in lieu of using Judd-Ofelt theory, known in the art, because the corrected emission spectrum from a spectrofluorometer is representative of relative photon flow vs. wavelength. For example, the ⁵Do→ ⁷Fi transition can be considered to be chemically insensitive to changes in surrounding environment. Under the assumption that the relative magnetic dipole strength is both wavelength independent and proportional to the dipole strength of, e.g. the ⁵Do→ ¾ transition, the shape of the emission spectrum of an lanthanide ions, e.g. Eu³⁺, center can be related to its radiative lifetime via:

wherein z_R is the radiative lifetime, A_MB (known in the art as approximately 14.65 s^"1) is the spontaneous emission probability of the ⁵Do→ ⁷Fi transition for an Eu³⁺ center in vacuum, n is the refractive index of the medium, and IMD is the ratio of the corrected emission spectrum of the material to the emission of just the magnetic dipole transition. Just as above, the same or similar calculations can be made for other lanthanide metals.

[0057] The composition may have an experimental lifetime measurement of from 0.4 to 1.6, from 0.5 to 1.5, from 0.6 to 1.4, from 0.7 to 1.3, from 0.8 to 1.2, from 0.9 to 1.1, or 1.0, milliseconds, or any value or range of values therebetween, as determined using a Flurolog3 (Horiba Scientific) spectrofluorometer according to the method described below.

[0058] Experimental lifetimes can be collected using a Horiba Jobin-Yvon Fluorolog 3 spectrofluorometer equipped with a 3 slit double grating emission monochromator (2.1 nm/mm, 1200 grooves/mm) and adapted for time-correlated single photon counting, using a 395 nm SpectraLED light emitting diode with a 100 us pulse width. The experimentally collected decay curves are typically analyzed the commercially available DAS6 decay analysis software package, using a 1 parameter exponential fit. Goodness of fit can be determined by minimizing the reduced Chi- squared function and inspection of the weighted residuals. Each decay curve can count at least 10,000 points and data reported tends to be from three independent measurements. Typical sample concentrations typically include 5% wt solids in solvents containing toluene and optionally 1-butanol to improve solubility. Measurements can be performed in 1 cm square quartz cuvettes, or equivalents. [0059] FTIR spectra can be recorded between 4000 cm^"1 and 400 cm^"1 with a resolution of 4 cm^"1 on a Nicolet 6700 FT-IR spectrometer. The spectra can be collected by directly measuring powder samples via attenuated total reflection (ATR) using a ZnSe or diamond cell.

[0060] This disclosure also provides a silicone composition including the polyheterosiloxane composition and a silicone fluid, e.g. a non-curable silicone fluid, as appreciated in the art. The silicone fluid is typically PDMS but is not limited in this way. In various embodiments, the silicone fluid has a viscosity at 25 °C of from about 0.001 to about 50 Pa- s, typically from about 0.02 to about 10 Pa- s, and more typically from about 0.05 to about 5 Pa- s. The silicone fluid can be linear, branched, cyclic, or a mixture thereof. Mixtures of the aforementioned fluids may also be used. Many of the linear, branched, and cyclic silicone fluids have melting points below about 25° C. Such materials are also commonly described as silicone liquids, silicone fluids, or silicone oils. A detailed description of non-limiting silicone fluids can be found in many references, including "Chemistry and Technology of Silicones" by W. Knoll, Academic Press, 1968, which, in one embodiment, is incorporated herein by reference relative to the silicone fluids.

[0061] Non-limiting examples of linear silicone fluids suitable for use herein include trimethylsiloxy-terminated dimethylsiloxane fluids sold by Dow Corning Corporation under the trade name "Dow Corning® 200 Fluids". These silicone fluids are manufactured to yield essentially linear oligomers and/or polymers typically having a viscosity of from 0.001 to about 50 Pa- s at 25 °C. Such fluids are primarily linear but can include cyclic and/or branched structures. In one embodiment, the silicone fluid is a trimethylsiloxy-terminated polydimethylsiloxane having a viscosity of about 0.1 Pa- s at 25 °C.

[0062] Additional non-limiting examples of suitable cyclic silicone fluids include the cyclic polydimethylsiloxanes sold by Dow Corning Corporation under the trade names "Dow Corning® 244, 245, 344, and 345 Fluids", depending on the relative proportions of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Mixtures of the straight-chain and cyclic dimethyl may also be utilized. Even additional non-limiting examples of suitable silicone fluids are Me₃SiO[(OSiMe₃)2SiO]SiMe3 and Me₃SiO[(OSiMe₃)MeSiO]SiMe₃. [0063] The polyheterosiloxane composition is not particularly limited relative to an amount present in the silicone composition. In various embodiments, the polyheterosiloxane composition in present in the silicone composition in amounts from 50 to 1,000, from 100 to 950, from 150 to 900, from 200 to 850, from 250 to 800, from 300 to 750, from 350 to 700, from 400 to 650, from 450 to 600, or from 500 to 550, parts by weight per one million parts by weight of the silicone composition. In other embodiments, the polyheterosiloxane composition in present in the silicone composition in amounts from 0.1 to 1, from 0.2 to 0.9, from 0.3 to 0.8, from 0.4 to 0.7, or from 0.5 to 0.6, parts by weight per 100 parts by weight of the silicone composition. In still other embodiments, the polyheterosiloxane composition in present in the silicone composition in amounts from 1 to 10, 2 to 9, 3 to 8, 4 to 7, or 5 to 6, parts by weight per 100 parts by weight of the silicone composition. In further embodiments, the polyheterosiloxane composition in present in the silicone composition in amounts from 10 to 80, from 15 to 75, from 20 to 70, from 25 to 65, from 30 to 60, from 35 to 55, from 40 to 50, or from 45 to 50, parts by weight per 100 parts by weight of the silicone composition.

Photosensitizer:

[0064] In various embodiments, at least one of the metals (Ml) and/or (M2) is a lanthanide metal and the silicone composition also includes a photosensitizer. The photosensitizer may impart a larger peak emission intensity to the polyheterosiloxane composition and/or silicone composition at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 to 470, 340 to 460, 350 to 450, 360 to 440, 370 to 430, 380 to 420, 390 to 410, or about 400, nm, as compared to a control polyheterosiloxane composition and/or control silicone composition, respectively, free of the photosensitizer.

[0065] The photosensitizer may be present in the polyheterosiloxane composition, or in the silicone composition, in an amount of less than 3 moles of photosensitizer per one mole of the lanthanide metal. In other words, the photosensitizer may be present in an amount greater than zero but less than 3 moles of the photosensitizer per one mole of the lanthanide metal. In various embodiments, the photosensitizer is present in amounts of less than 2.5, less than 2, less than 1.5, less than 1, less than 0.75, less than 0.5, less than 0.25, less than 0.1, less than 0.05, less than 0.01, less than 0.005, less than 0.001, less than 0.0005, less than 0.0004, etc. moles of photosensitizer per one mole of the lanthanide metal. In other embodiments, the photosensitizer is present in amounts of from 0.0001 to 0.0002, 0.0001 to 0.0003, 0.0001 to 0.0004, 0.0001 to 0.0005, 0.0001 to 0.0006, 0.0001 to 0.0007, 0.0008 to 0.0009, 0.0001 to 0.001, 0.0004 to 0.004, 0.001 to 0.1, 0.001 to 0.009, 0.001 to 0.008, 0.001 to 0.007, 0.001 to 0.006, 0.001 to 0.005, 0.001 to 0.004_s0.001 to 0.003, 0.001 to 0.002, 0.01 to 0.09, 0.01 to 0.08, 0.01 to 0.07, 0.01 to 0.06, 0.01 to 0.05, 0.01 to 0.04, 0.01 to 0.03, 0.01 to 0.02, 0.1 to 0.9, 0.1 to 0.8, 0.1 to 0.7, 0.1 to 0.6, 0.1 to 0.5, 0.1 to 0.4, 0.1 to 0.3, or 0.1 to 0.2, moles of photosensitizer per one mole of the lanthanide metal.

[0066] The photosensitizer is not particularly limited. In one embodiment, the photosensitizer is chosen from (i) a β-diketone, (ii) a β -diketonate, (iii) a salicylic acid, (iv) an aromatic carboxylic acid, (v) an aromatic carboxylate, (vi) a polyaminocarboxylic acid, (vii) a polyaminocarboxylate, (viii) a N-heterocyclic aromatic compound, (ix) a Schiff base, (x) a phenol, (xi) an aryloxide, and combinations thereof. In various other embodiments, the photosensitizer is (i) a β - diketone, or (ii) a β-diketonate, or (iii) a salicylic acid, or (iv) an aromatic carboxylic acid, or (v) an aromatic carboxylate, or (vi) a polyaminocarboxylic acid, or (vii) a polyaminocarboxylate, or (viii) a N-heterocyclic aromatic compound, or (ix) a Schiff base, or (x) a phenol, or (xi) an aryloxide, or a combination of one or more of the aforementioned compounds. In still other embodiments, the photosensitizer is a β - diketone or a β -diketonate. In additional embodiments, the photosensitizer is an aromatic carboxylic acid or aromatic carboxylate. Alternatively, the photosensitizer may be a salicylic acid or a salicylate. The photosensitizer may be any one of the aforementioned types of compounds and/or may be further defined as a mixture of two or more of any of the aforementioned types of compounds.

[0067] Non-limiting examples of suitable photosensitizers include 1,3- diphenylpropandione; 2-thenoyltrifluoroacetone, 2-dithenoylpropandione, l-phenyl-3- (2-fluoryl)propandione; l-(4-biphenyl)-3-(2-fluoryl)propandione; l-(2-naphtyl)-3-(2- fluoryl)propandione; l-(l-naphtyl)-3-(2-fluoryl)propandione; l-(2,3,4,5- tetrafluorophenyl)-3-(2-fluoryl)propandione; l l-(2-fluoryl)-4,4,4-trifluorobutane-l,3- dione; l-(2,3,4,5-tetrafluorophenyl)-3-(2-fluoryl)propandione; l-(2,4,6- trifluorophenyl)-3-(2-fluoryl)propandione; l-(3,4,5-trifluorophenyl)-3-(2- fluoryl)propandione; l-(5-bromothiophen-2-yl)-4,4,4-trifluorobutane-l,3-dione; 1- (4' -methoxy-4-biphenyl)-4,4,4-trichlorobutane- 1 ,3-dione; 9-hydroxyphenalen- 1 -one, tropolone, diethyl 2-hydroxyazulene-l,3-dicarboxylates; benzoic acid, 4- (octyloxy)benzoic acid, 4-(t-butyl)benzoic acid, 2-ethoxybezoic acid, 3-ethoxybezoic acid, 4-ethoxybezoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4- methoxybenzoic acid, 4-butoxybenzoic acid, 1 -naphthoic acid, 2-naphthoic acid, biphenyl-2-carboxylic acid, biphenyl-4-carboxylic acid, 9-fluorenone-l-carboxylic acid, fluorene-9-carboxylic acid, fluorobenzoic acid, chlorobenzoic acid, 2- hydroxybenzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 3,5-dimethylbenzoic acid, 4-cyanobenzoic acid; 2,2'-bipyridines, 4,4'- bipyridines, 2,2',2"-bipyridines, 1,10-phenantrolines, 1,8-naphthylridines, benzimidazole-pyridines, bis(benzimidazol)pyridines, porphyrines, macrocyclic imines, H2Salen, 8-hydroxyquinolines; 5,7-dihalo-8-hydroxyquinolines; benzimidazole substituted 8-hydroxyquinolines, EDTA, DPTA, DOTA, and combinations thereof.

[0068] Additional non-limiting examples of suitable photosensitizers may have one or more of the structures below: Additional non-limiting examples of suitable photosensitizers may have one or more of the structures below:

Wherein Rl = 2-fluoryl, R2 = 4-biphenyl; 1-naphthyl; 2-naphthyl; phenyl; trifluoromethyl; 2,3,4,5-tetrafluorophenyl; 2,4,6-trifluorophenyl; 3,4,5- trifluorophenyl; and R3 = H;

Wherein Rl= trifluoromethyl; R2 = 5-bromo-2-thiophene; and R3 = H;

Wherein Rl = trichloromethyl; R2 = 4'-methoxy-4-biphenyl; and R3 = H; or

Wherein Rl, R2 = phenyl, naphthyl, biphenyl, fluoryl, or perfluoroalkyl, and R3=H; or

R = alkyl or aryl

R: F, CI, Br, I, ORl (Rl: alkyl, aryl), N02, aryl, alkyl, NRl, OH, COOH, COORl

X: H, alkyl, aryl, COOH, COORl O

O H

N=0

R: F, CI, Br, I, COOH, COORl

R: F, CI, Br, I, ORl (Rl : alkyl, aryl), N02, aryl, alkyl, NRl, OH, COOH, COORl

R = Μθ, ΟΜθ, CI

R: F, CI, Br, I, ORl (Rl : alkyl, aryl), N02, aryl, alkyl, NRl, OH, COOH, COORl

Curable Silicone:

[0069] The silicone composition may also include a (II) curable silicone. The curable silicone is not particularly limited and may be further defined as a curable silicone fluid, gel, etc. Examples of curable silicones include, but are not limited to, hydrosilylation-curable silicones, condensation-curable silicones, radiation-curable silicones, peroxide-curable silicones, and acid or amine cured silicones, e.g. epoxy curable silicones.

[0070] The curable silicone can be further described as curing to form a thermoset silicone polymer or a thermoplastic silicone polymer. Typically, as used herein and below, the term "thermoplastic polymer" describes a silicone polymer that has the physical property of converting to a fluid (flowable) state when heated and of becoming rigid (non-flowable) when cooled. Although thermoplastic polymers do not "cure" as that term is typically understood in the art, for purposes of this disclosure, the terminology "curable" or "cure" can describe the hardening of the thermoplastic polymer. Also, the term "thermoset polymer" may describe a cured (i.e., cross-linked) silicone polymer that does not convert to a fluid state on heating. As used herein and below, the term "thermoset polymer" typically describes a silicone polymer having the property of becoming permanently rigid (non-flowable) when cured (i.e., cross- linked).

[0071] A hydrosilylation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule; an organosilicon compound in an amount sufficient to cure the organopolysiloxane, wherein the organosilicon compound has an average of at least two silicon-bonded hydrogen atoms or silicon-bonded alkenyl groups per molecule capable of reacting with the silicon-bonded alkenyl groups or silicon- bonded hydrogen atoms in the organopolysiloxane; and a catalytic amount of a hydrosilylation catalyst.

[0072] A condensation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule and, optionally, a cross-linking agent having silicon-bonded hydrolysable groups and/or a condensation catalyst. In one embodiment, the cross-linking agent has the formula R²qSiX4__q, wherein R2 is a Ci to Cg hydrocarbyl group or a Cj to Cg halogen-substituted hydrocarbyl group, X is a hydrolysable group, and q is 0 or 1.

[0073] A radiation-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded radiation-sensitive groups per molecule and, optionally, a cationic or free-radical photoinitiator depending on the nature of the radiation- sensitive groups in the silicone organopolysiloxane.

[0074] A peroxide-curable silicone typically includes an organopolysiloxane having silicon-bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.

[0075] An epoxy-curable silicone typically includes an organopolysiloxane having an average of at least two silicon-bonded epoxy-functional organic groups. Typically, before curing, a proton source, such as an amine, SiH, acid generator, or a cationic photo-acid generator, are utilized.

[0076] The silicone composition including (I) and (II) can be cured by exposing the silicone composition to ambient temperature, elevated temperature, moisture, or radiation, depending on the type of curable silicone.

[0077] When the (II) curable silicone is a hydrosilylation-curable silicone, the silicone composition (which includes (I) and (II)) can be cured by exposing the silicone composition to a temperature of from room temperature (-23 + 2 °C) to 250 °C, alternatively from room temperature to 150 °C, alternatively from room temperature to 115 °C, at atmospheric pressure. The silicone composition is generally heated for a length of time sufficient to cure (cross-link) the organopolysiloxane. For example, the film is typically heated at a temperature of from 100 to 150 °C for a time of from 0.1 to 3 h.

[0078] When the (II) curable silicone is a condensation-curable silicone, the conditions for curing the silicone composition (which includes (I) and (II)) depend on the nature of the silicon-bonded groups in the organopolysiloxane. For example, when the organopolysiloxane contains silicon-bonded hydroxy groups, the silicone composition can be cured (i.e., cross-linked) by heating the silicone composition. The silicone composition can typically be cured by heating it at a temperature of from 50 to 250 °C, for a period of from 1 to 50 h. When the (II) condensation-curable silicone comprises a condensation catalyst, the silicone composition can typically be cured at a lower temperature, e.g., from room temperature (-23 ± 2 °C) to 150 °C.

[0079] When the (II) curable silicone is a condensation-curable silicone comprising an organopolysiloxane having silicon-bonded hydrogen atoms, the silicone composition (which includes (I) and (II)) can be cured by exposing the silicone composition to moisture or oxygen at a temperature of from 100 to 450 °C for a period of from 0.1 to 20 h. When the (II) condensation-curable silicone contains a condensation catalyst, the silicone composition can typically be cured at a lower temperature, e.g., from room temperature (-23 ± 2 °C) to 400 °C.

[0080] Further, when the (II) curable silicone is a condensation-curable silicone comprising an organopolysiloxane having silicon-bonded hydroly sable groups, the silicone composition (which includes (I) and (II)) can be cured by exposing the silicone composition to moisture at a temperature of from room temperature (-23 + 2 °C) to 250 °C, alternatively from 100 to 200 °C, for a period of from 1 to 100 h. For example, the silicone composition can typically be cured by exposing it to a relative humidity of 30% at a temperature of from about room temperature (-23 + 2 °C) to 150 °C, for a period of from 0.5 to 72 h. Cure can be accelerated by application of heat, exposure to high humidity, and/or addition of a condensation catalyst to the silicone composition.

[0081] When the (II) curable silicone is a radiation-curable silicone, the silicone composition (which includes (I) and (II)) can be cured by exposing the silicone composition to an electron beam. Typically, the accelerating voltage is from about 0.1 to 100 keV, the vacuum is from about 10 to 10-3 Pa, the electron current is from about 0.0001 to 1 ampere, and the power varies from about 0.1 watt to 1 kilowatt. The dose is typically from about 100 microcoulomb/cm^ to 100 coulomb/cm^, alternatively from about 1 to 10 coulombs/cm^. Depending on the voltage, the time of exposure is typically from about 10 seconds to 1 hour.

[0082] Also, when the (II) radiation-curable silicone further includes a cationic or free radical photoinitiator, the silicone composition (which includes (I) and (II)) can be cured by exposing it to radiation having a wavelength of from 150 to 800 nm, alternatively from 200 to 400 nm, at a dosage sufficient to cure (cross-link) the organopolysiloxane. The light source is typically a medium pressure mercury-arc lamp. The dose of radiation is typically from 30 to 1,000 mJ/cm^, alternatively from

50 to 500 mJ/cm^. Moreover, the silicone composition can be externally heated during or after exposure to radiation to enhance the rate and/or extent of cure.

[0083] When the (II) curable silicone is a peroxide-curable silicone, the silicone composition (which includes (I) and (II)) can be cured by exposing it to a temperature of from room temperature (-23 ± 2 °C) to 180 °C, for a period of from 0.05 to 1 h. [0084] When the (II) curable silicone is an epoxy-curable silicone, the silicone composition (which includes (I) and (II)) can be cured by exposing it to a temperature of from room temperature (-23 ± 2 °C) to 180 °C, for a period of from 0.05 to 1 h.

[0085] The (II) curable silicone is typically present in an amount of at least about 50 weight percent based on a total weight of the silicone composition. In various embodiments, the (II) curable silicone is present in an amount of at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or 99, weight percent based on a total weight of the silicone composition. In other embodiments, the (II) curable silicone is present in an amount of from 95 to 99.9, from 90 to 95, from 85 to 90, from 80 to 85, from 75 to 80, from 70 to 75, from 65 to 70, from 60 to 65, from 55 to 60, from 50 to 55, from 90 to 99.9, from 85 to 95, from 75 to 85, from 65 to 75, from 55 to 65, from 70 to 95, from 80 to 95, from 20 to 55, 25 to 50, 30 to 45, or 35 to 40, weight percent based on a total weight of the silicone composition. All amounts, and ranges of amounts, both whole and fractional, within the ranges set forth above are herein expressly contemplated but are not described for the sake of brevity.

[0086] The (II) curable silicone may be utilized as a single component or as a series of components, e.g. as a one part, two part, or multi-part component system. For example, various compounds in the curable silicone may be segregated into "A" and "B" portions such that when the "A" and "B" portions are combined, the curable silicone can cure.

Method of Formin2 the Composition:

[0087] This disclosure also provides a method of forming the polyheterosiloxane composition. The method includes the step of reacting (Α') a metal (M3) alkoxide, (Β') an optional hydrolyzable metal (M4) salt, (C) a silicon-containing material having silicon-bonded hydroxy groups, and (D) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β'). The method may also include one or more steps as described in WO2011/002826, which is expressly incorporated herein by reference. The method may also include the step of introducing the photosensitizer to one or more components (A)-(F), as described above or below.

[0088] It is to be understood that (Α'), optionally (Β'), (C), and (D) may react together in any order. For example, (Α'), optionally (Β'), (C')_> and (D) may react individually or with more of each other batch wise (e.g. simultaneously) and/or sequentially. One or more portions of (Α'), optionally (Β'), (C), and (D) may react individually or with more of portions of each other batch wise (e.g. simultaneously) and/or sequentially. (Β') may not be utilized and alkoxides may be utilized in the absence of a hydrolyzable metal. In another embodiment, (Β') is utilized, e.g. with an alkoxide.

[0089] The (Α') metal (M3) alkoxide is not particularly limited and may be further defined as one or a mixture of alkoxides of one or more of the metals described above. One metal (M3) alkoxide, two different alkoxides of the same metal (M3), two alkoxides of different metals (M3), or a plurality of alkoxides of one or more metals (M3), may be utilized.

[0090] The metal (M3) is not particularly limited but is typically is the same as (Ml), e.g. a lanthanide metal or a non-lanthanide metal. The metal (M3) of the metal alkoxide may be independently selected and may be the same as (Ml) or (M2) or may be different.

[0091] In one embodiment, one of (M3) and (M4) is a lanthanide metal and the other of (M3) and (M4) is a non-lanthanide metal chosen from aluminum (Al), zirconium (Zr), and combinations thereof. In this embodiment, (M3) may be the same as (Ml). The metal (M3) of the metal alkoxide may be independently selected and may be the same as (Ml) or (M2) or may be different.

[0092] The metal (M3) alkoxide may have the general formula (I) RljJV130_n X_D(OR2) vl-k-p-2n. Iⁿ Formula (I), subscript vl is the oxidation state of metal (M3), typically from 1 to 7, 1 to 5, or 2 to 4, subscript k is typically a value from 0 to 3, alternatively 0 to 2, and alternatively 0. subscript n is typically a value from 0 to 2, alternatively 0 to 1, and alternatively 0, and subscript p is typically a value from 0 to 3, alternatively 0 to 2, and alternatively 0. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0093] R1 is typically a monovalent alkyl group having from 1 to 18, from 2 to 17, from 3 to 16, from 4 to 15, from 5 to 14, from 6 to 13, from 7 to 12, from 8 to 11, from 9 to 10, or from 1 to 8 carbon atoms or any value or range of values therebetween. Non-limiting examples of the alkyl group of R1 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl groups. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0094] Each is typically an independently selected monovalent alkyl group having from 1 to 6, 2 to 5, or 3 to 4 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) -(R^OijR^, where j is a value from 1 to 4 and alternatively 1 to 2. Each R^ is typically an independently selected divalent alkylene group having from 2 to 6, 3 to 5, or 3 to 4, carbon atoms. Each R4 is typically an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6, 2 to 5, or 3 to 4 carbon atoms. Non-limiting examples of the alkyl groups of R^ include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and hexyl groups. Non-limiting examples of the aryl groups of R^ include phenyl and benzyl. Non-limiting examples of the divalent alkylene group include ^"CH2CH2- and - CH2CH(CH3)- . Non-limiting examples of the alkyl groups having from 1 to 6 carbon atoms of R4 are as described above for R2. Non-limiting examples of the polyether group of Formula (VI) include methoxyethyl, methoxypropyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, methoxyethoxyethyl, and ethoxyethoxyethyl groups. Alternatively, R^ is typically an alkyl group having from 1 to 6 carbon atoms e.g. a methyl, ethyl, propyl, and butyl group, or a propyl and butyl group. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0095] X is typically chosen from carboxylate ligands, organosulfonate ligands, organophosphate ligands, β-diketonate ligands, and chloride ligands, alternatively carboxylate ligands and β-diketonate ligands. The carboxylate ligands for X typically have a formula Rl5cOO^~ where R!5 is chosen from hydrogen, alkyl groups, alkenyl groups, and aryl groups. Non- limiting examples of alkyl groups for R!5 include alkyl groups having from 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms as described above for R1. Non-limiting examples of alkenyl groups for R!5 include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, 2-propenyl, allyl, hexenyl, and octenyl groups. Non-limiting examples of aryl groups for R!5 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and benzyl groups. Alternatively, R!5 is methyl, 2-propenyl, allyl, and phenyl, β-diketonate ligands for X can have the following structures:

where R^, R!8, and R21 are typically chosen from monovalent alkyl and aryl groups. Non-limiting examples of alkyl groups for R^, R!8, and R21 include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 4 carbon atoms such as methyl, ethyl, trifluoromethyl, and t-butyl groups. Non-limiting examples of aryl groups for Rl6, R18₅ and R21 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups. R!9 is typically chosen from alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups for R19 include CI to C18 alkyl groups, alternatively CI to C8 alkyl groups such as methyl, ethyl, propyl, hexyl and octyl groups. Non-limiting examples of alkenyl groups for R19 include alkenyl groups having from 2 to 18 carbon atoms, alternatively C2 to C8 carbon atoms such as allyl, hexenyl, and octenyl groups. Non- limiting examples of aryl groups for R!9 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups. R! and R²⁰ are typically hydrogen or alkyl, alkenyl, and aryl groups. Non-limiting examples of alkyl groups for R! and R^O include alkyl groups having from 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms such as methyl and ethyl groups.

Non-limiting examples of alkenyl groups for R!7 and R^O include alkenyl groups having from 2 to 18 carbon atoms, alternatively 2 to 8 carbon atoms such as vinyl, allyl, hexenyl, and octenyl groups. Non-limiting examples of aryl groups for R! and R20 include aryl groups having from 6 to 18 carbon atoms, alternatively 6 to 8 carbon atoms such as phenyl and tolyl groups. Rl6, R17₅ R18₅ R19₅ R20_{5 an(}j R21 _{are eacn} independently selected and can be the same or different from each other. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[0096] Non-limiting examples of metal alkoxides described by Formula (I) include titanium tetrapropoxides, titanium butoxide, titanium tetrabutoxides, zirconium tetrapropoxides, and zirconium tetrabutoxides from DuPont, aluminum tripropoxides, aluminum tributoxides, aluminum phenoxide, antimony (III) ethoxide, barium isopropoxide, cadmium ethoxide, cadmium methoxide, cadmium methoxyethoxide, chromium (III) isopropoxide, copper (II) ethoxide, copper (II) methoxyethoxyethoxide, gallium ethoxide, gallium isopropoxide, diethyldiethoxy germane, ethyltriethoxygermane, methyltriethoxygermane, tetra-n- butoxygermane, hafnium ethoxide, hafnium 2-ethylhexoxide, hafnium 2- methoxymethyl-2-propoxide, indium methoxyethoxide, iron (III) ethoxide, magnesium ethoxide, magnesium methoxyethoxide, magnesium n-propoxide, molybdenum (V) ethoxide, niobium (V) n-butoxide, niobium (V) ethoxide, cerium (IV) t-butoxide, cerium (IV) isopropoxide, cerium (IV) ethylthioethoxide, cerium (IV) methoxyethoxide, strontium isopropoxide, strontium methoxypropoxide, tantalum (V) ethoxide, tantalum (V) methoxide, tantalum (V) isopropoxide, tantalum tetraethoxide diemthylaminoethoxide, di-n-butyldi-n-butoxytin, di-n-butyldimethoxytin, tetra-t- butoxytin, tri-n-butylethoxytin, titanium ethoxide, titanium 2-ethylhexoxide, titanium methoxide, titanium methoxypropoxide, titanium n-nonyloxide, tungsten (V) ethoxide, tungsten (VI) ethoxide, vanadium triisobutoxide oxide, vanadium triisopropoxide oxide, vanadium tri-n-propoxide oxide, vanadium oxide tris (methoxyethoxide), zinc methoxyethoxide, zirconium ethoxide, zirconium 2- ethylhexoxide, zirconium 2-methyl-2-butoxide, and zirconium 2-methoxymethyl-2- propoxide, aluminum s-butoxide bis(ethylacetoacetate), aluminum di-s-butoxide ethylacetoacetate, aluminum diisopropoxide ethylacetoacetate, aluminum 9- octdecenylacetoacetate diisopropoxide, tantalum (V) tetraethoxide pentanedionate, titanium allylacetoacetate triisopropoxide, titanium bis(triethanolamine) diisopropoxide, titanium chloride triisopropoxide, titanium dichloride diethoxide, titanium diisopropoxy bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), titanium methacrylate triisopropoxide, titanium methacryloxyethylacetoacetate triisopropoxide, titanium trimethacrylate methoxyethoxyethoxide, titanium tris(dioctylphosphato)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, zirconium (bis-2,2' -(alloxymethyl)- butoxide)tris(dioctylphosphate), zirconium diisopropoxide bis(2,2,6,6-tetramethyl- 3,5-heptanedionate), zirconium dimethacrylate dibutoxide, zirconium methacryloxyethylacetoacetate tri-n-propoxide, and combinations thereof. (Α') may be chosen from titanium tetraisopropoxide, titanium butoxide, titanium tetrabutoxide, zirconium tetrabutoxide, or aluminum sec -butoxide.

[0097] The optional (B ') hydrolyzable metal (M4) salt is not particularly limited and may be further defined as one or a mixture of salts of one or more of the metals described above. One hydrolyzable metal (M4) salt, two different salts of the same metal (M4), two salts of different metals (M4), or a plurality of salts of one or more metals (M4), may be utilized.

[0098] Typically, the hydrolyzable metal (M4) is the same as the (M2). The hydrolyzable metal (M4) may be a lanthanide metal or a non-lanthanide metal. The hydrolyzable metal (M4) may be the same as (Ml) or (M2) or metal (M3) or may be different. In addition, hydrolyzable metal (M4) may be independently selected and may any one of the aforementioned options for (Ml) and/or (M2) and/or metal (M3). However, at least one of metal (M3) and hydrolyzable metal (M4) is typically a lanthanide metal.

[0099] Additional non-limiting examples of (Β') include but are not limited to lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, scandium acetate, yttrium acetate, lutetium acetate, hafnium acetate, vanadium acetate, niobium acetate, tantalum acetate, chromium acetate, molybdenum acetate, tungsten acetate, manganese acetate, technetium acetate, rhenium acetate, iron acetate, ruthenium acetate, osmium acetate, cobalt acetate, rhodium acetate, iridium acetate, nickel acetate, palladium acetate, platinum acetate, copper acetate, silver acetate, zinc acetate, cadmium acetate, mercury acetate, aluminum acetate, gallium acetate, indium acetate, thallium acetate, tin, lead acetate, antimony acetate, bismuth acetate, lanthanum acetate, cerium acetate, praseodymium acetate, neodymium acetate, promethium acetate, samarium acetate, europium acetate, gadolinium acetate, terbium acetate, dysprosium acetate, holmium acetate, erbium acetate, thulium acetate, ytterbium acetate, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, rubidium acetylacetonate, cesium acetylacetonate, beryllium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, strontium acetylacetonate, barium acetylacetonate, scandium acetylacetonate, yttrium acetylacetonate, lutetium acetylacetonate, titanium acetylacetonate, zirconium acetylacetonate, hafnium acetylacetonate, vanadium acetylacetonate, niobium acetylacetonate, tantalum acetylacetonate, chromium acetylacetonate, molybdenum acetylacetonate, tungsten acetylacetonate, manganese acetylacetonate, technetium acetylacetonate, rhenium acetylacetonate, iron acetylacetonate, ruthenium acetylacetonate, osmium acetylacetonate, cobalt acetylacetonate, rhodium acetylacetonate, iridium acetylacetonate, nickel acetylacetonate, palladium acetylacetonate, platinum acetylacetonate, copper acetylacetonate, silver acetylacetonate, zinc acetylacetonate, cadmium acetylacetonate, mercury acetylacetonate, aluminum acetylacetonate, gallium acetylacetonate, indium acetylacetonate, thallium acetylacetonate, tin acetylacetonate, lead acetylacetonate, antimony acetylacetonate, lanthanum acetylacetonate, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, promethium acetylacetonate, samarium acetylacetonate, europium acetylacetonate, gadolinium acetylacetonate, terbium acetylacetonate, dysprosium acetylacetonate, holmium acetylacetonate, erbium acetylacetonate, thulium acetylacetonate, ytterbium acetylacetonate, aluminum acrylate, aluminum methacrylate, aluminum stearate, barium methacrylate, barium acrylate, bismuth 2- ethylhexanoate, calcium methacrylate, calcium acrylate, calcium undecylenate, copper (II) methacrylate, copper (II) 2-ethylhexanoate, hafnium 2- ethylhexanoate, iron methacrylate, iron acrylate, lead methacrylate, lead acrylate, lead 2-ethylhexanoate, lithium methacrylate, lithium acrylate, magnesium methacrylate, magnesium acrylate, potassium methacrylate, potassium acrylate, potassium sulfopropylmethacrylate, potassium sulfopropylacrylate, cerium (III) 2- ethylhexanoate, europium (III) acrylate, europium (III) methacrylate, neodymium methacrylate, neodymium neodecanoate, yttrium methacrylate, silver acrylate, silver methacrylate, silver neodecanoate, sodium acrylate, sodium methacrylate, sodium allylsulfonate, strontium acrylate, strontium methacrylate, bis(2-ethylhexanoate)tin, bis(neodecanoate)tin, n-butyltris(2-ethylhexanoate)tin, di-n-butylbis(2- ethylhexanoate)tin, zinc acrylate, zinc methacrylate, zinc neodecanoate, zinc undecanoate, zinc 2-ethylhexanoate, zirconium methacrylate, copper sulphate, zinc chloride, silver nitrate, iron nitrate, nickel nitrate, zinc nitrate, acryloxytri-n- butyltin, acryloxytriphenyltin, di-n-butylbis(2,4- pentanedionate)tin, di-n- butyldiacetoxytin, di-n-butyldiacrylatetin, di-n-butyldilauryltin, di-n- butyldimethacrylatetin, di-n-butyldineodecanoatetin, dimethylbis(2,4- pentanedionate)tin, dimethyldineodecanoatetin, dioctyldilauryltin, methacryloxytri-n- butyltin, tri-n-butylacetoxytin, and tri-n-butylbenzoyloxytin. zinc acetate dihydrate, nickel acetate tetrahydrate, magnesium acetate tetrahydrate, zinc nitrate hexahydrate, and copper sulphate pentahydrate, benzoates thereof, alkylbenzoates thereof, alkyloxybenzoates thereof, triphenylacetates thereof, and/or combinations thereof.

[00100] The optional (B ') hydrolyzable metal (M4) salt may be further described as

(B' l) a non-hydrated metal salt having a general formula (IV) R^_eM4(Z)(_v2__e)/w ^or

(B'2) a hydrated metal salt having a general formula (V) M4(Z)_v2/_w-xH20. v2 is the oxidation state of hydrolyzable metal (M4) and w is the oxidation state of ligand Z where Z is typically independently chosen from carboxylates, β-diketonates, fluoride, chloride, bromide, iodide, organic sulfonate, nitrate, nitrite, sulphate, sulfite, cyanide, phosphites, phosphates, organic phosphites, organic phosphates, and oxalate. Each is typically an independently selected alkyl group having 1 to 18 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, or an aryl group having from 6 to 8 carbon atoms while e is typically a value from 0 to 3 and x is typically a value from 0 to 12, or from 0.5 to 12, and typically describes the average number of ]¾0 molecules associated with each metal salt molecule. The oxidation state of hydrolyzable metal (M4) may be as described above or may be different. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00101] In Formulas (IV) and (V), subscript w is the oxidation state of ligand Z and typically can range from 1 to 3, alternatively from 1 to 2. The Z group in Formulas (IV) and (V) describes various counter ligands that may be attached to hydrolyzable metal (M4). Typically, each Z is independently chosen from carboxylate ligands, β- diketonate ligands, fluoride ligand, chloride ligand, bromide ligand, iodide ligand, organic sulfonate ligands, nitrate ligand, nitrite ligand, sulphate ligand, sulfite ligand, cyanide ligand, phosphate ligand, phosphite ligand, organic phosphite ligands, organic phosphate ligands, and oxalate ligand. The carboxylate ligands and β-diketonate ligands for Z may be as described above for X. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00102] The carboxylate ligands may also be chosen from acrylate, methacrylate, butylenate, ethylhexanoate, undecanoate, undecylenate, dodecanoate, tridecanoate, pentadecanoate, hexadecanoate, heptadecanoate, octadecanoate, cis-9-octadecylenate (C18), cis- 13-docoylsenoate (C22). The carboxylate ligand may be undecylenate or ethylhexanoate. Alternatively, the organic sulfonate ligands for Z may have a formula

R22SC>3^", where R^2 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Examples of alkyl groups, alkenyl groups and aryl groups are as described above for R.15. Alternatively R^2 is tolyl, phenyl, or methyl.

[00103] The organic phosphate ligands for Z typically have a formula (R23())2 Ρ⁽¾^~ or R23()- PO32-, where R^3 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups, alkenyl groups and aryl groups are as described above for R!5. Alternatively R^3 may be phenyl, butyl, or octyl.

[00104] Organic phosphite ligands for Z may have a formula (R24())2 PO^~ or R2 ( P02^^", where R^4 is chosen from monovalent alkyl groups, alkenyl groups and aryl groups. Non-limiting examples of alkyl groups, alkenyl groups and aryl groups are as described above for R!5. Alternatively R^4 may be phenyl, butyl, or octyl. Alternatively, Z in Formulas (IV) and (V) may be independently chosen from carboxylate ligands, β-diketonate ligands, nitrate ligands, sulphate ligands, and chloride ligands. Alternatively, Z may include carboxylate ligands and β-diketonate ligands.

[00105] In Formulas (IV) and (V), subscript e is typically a value from 0 to 3, alternatively from 0 to 2, and alternatively 0. In Formula (IV), R^ may be an independently selected alkyl group having 1 to 18 carbon atoms, an alkenyl group having from 2 to 8 carbon atoms, or an aryl group having from 6 to 8 carbon atoms.

Non-limiting examples of R^ are as described above for R^. In Formula (V), x may be a value from 0.5 to 12, and alternatively from 1 to 9. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00106] Examples of (Β') hydrolyzable metal salts described by Formula (IV) include but are not limited to lanthanum acetate, cerium acetate, praseodymium acetate, neodymium acetate, promethium acetate, samarium acetate, europium acetate, gadolinium acetate, terbium acetate, dysprosium acetate, holmium acetate, erbium acetate, thulium acetate, ytterbium acetate, lutetium acetate, lanthanum acetylacetonate, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, promethium acetylacetonate, samarium acetylacetonate, europium acetylacetonate, gadolinium acetylacetonate, terbium acetylacetonate, dysprosium acetylacetonate, holmium acetylacetonate, erbium acetylacetonate, thulium acetylacetonate, ytterbium acetylacetonate, lutetium acetylacetonate, and combinations thereof. Non-limiting examples of hydrated metal salts (BΊ) described by Formula (VI) include the hydrated versions of any of the metal salts as described above for (B'l).

[00107] In one embodiment, (Β') is chosen from (B'l) a non-hydrated metal salt having a general formula (IV) R^_eM4(Z)(_v2__e)/_w and (B'2) a hydrated metal salt having a general formula (V) M4(Z)_v2/_w-xH20, wherein (M4) is a lanthanide metal, v2 is the oxidation state of M4, w is the oxidation state of Z, Z is independently chosen from alkoxides, carboxylates, β-diketonates, chlorides, organic sulfonates, nitrates, and oxalates, each is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, or aryl group having from 6 to 18 carbon atoms, e is a value from 0 to 3 and x is a value from 0 to 12.

[00108] In another embodiment, (Α') and (Β') are reacted with water to form a mixed metal oxide solution including metal (M3)-0-(M4) oxo-bonds. This solution may then be reacted with (C) to form the composition, wherein the total amount of water added is between 50 and 200% of the amount theoretically necessary for the hydrolysis and condensation of all alkoxy groups and other hydrolyzable groups of (Α'), and optionally (Β'). The percent may be further described as mole or weight percent as a theoretical calculated stoichiometric amount.

[00109] Referring now to (C), it is a silicon-containing material having silicon- bonded hydroxy groups. The silicon-containing material can be (C' l) a siloxane having silicon-bonded hydroxy groups, (C'2) a silane having silicon-bonded hydroxy groups, or combinations thereof.

[00110] The (C' l) siloxane can be a disiloxane, trisiloxane, or polysiloxane, or combinations thereof. Similarly, the (C'2) silane can be a monosilane, disilane, trisilane, or polysilane or combinations thereof. The structure of the (C' l) siloxane or (C'2) silane can be linear, branched, cyclic, or resinous. Cyclosilanes and cyclosiloxanes typically have from 3 to 12 silicon atoms, alternatively from 3 to 10 silicon atoms, alternatively from 3 to 4 silicon atoms. In acyclic polysilanes and polysiloxanes, the silicon-bonded hydroxy groups can be located at terminal, pendant, or at both terminal and pendant positions.

[00111] Non-limiting examples of (C'l) siloxanes having silicon-bonded hydroxy groups include MQ resins, OH-functional polydialkylsiloxanes, polydimethylsiloxane, polyalkylphenylsiloxanes polyphenylmethyldisiloxanes, polyarylalkysiloxanes, polydiphenylsiloxanes, polydiarylsiloxanes, polytrifluorumethylsiloxanes, polydiphenylsiloxane dimethylsiloxane copolymers, polyarylsiloxanes, polytrifluoropropylmethylsiloxane, and combinations thereof.

[00112] Non-limiting examples of (C'2) silanes having silicon-bonded hydroxyl groups include phenylsilanetriol, diphenylsilanediol, phenylmethylsilanediol, dimethylsilanediol, trimethylsilanol, triphenylsilanol, phenyldimethoxysilanol, phenylmethoxysilanediol, methyldimethoxysilanol, methylmethoxysilanediol, phenyldiethoxysilanol, phenylethoxysilanediol, methyldiethoxysilanol, and methylethoxysilanediol, and combinations thereof.

[00113] In one embodiment, (C) is further defined a hydrolysis product of at least one of: (C'i) a organosiloxane, (C'ii) a silane, and combinations thereof. In this embodiment, the hydrolysis product is further defined as the product of water and at least one of (C'i), (C'ii), and combinations thereof. At least one of (C'i) and (C'ii) has a hydrolyzable group. In other words, (C'i) may have a hydrolyzable group, (C'ii) may have a hydrolyzable group, or both (C'i) and (C'ii) each have a hydrolyzable group. One or both of (C'i) and (C'ii) can have more than one hydrolyzable group.

[00114] The (C) hydrolysis product, i.e., the product formed from reaction with water, may include R⁵ _g(R⁶0)f(HO)_jSiO(4-₍f₊g_+j))/2 and/or hydrolyzed silane R⁵ _h(HO)_kSiZ'i, wherein, for example, R⁵ is hydrogen or a hydrocarbyl group. A hydrolyzed organosiloxane R⁵ _g(R⁶0)f(HO)_jSiO(4-₍f₊g_+j))/2 or hydrolyzed silane R⁵ _h(HO)_kSiZ'i can be used directly or diluted with aromatic solvents (toluene) and alcohol before added to a mixture of (Α') and optionally (Β').

[00115] One or both of (C'i) and/or (C'ii) may be treated with stoichiometric amounts of water containing catalytic amounts of a strong acid, e.g. HC1 or any "strong acid", or any highly diluted aqueous acid to initiate or promote hydrolysis. Formation of a hydrolysis product may be accelerated by mixing hydrolysable (C'i) or (C'ii) with highly diluted aqueous acid or sonication of a mixture of both. For example, a silane (C'ii), e.g. having a general formula (III) R⁵ _hSiZ'; (wherein Z' = CI and i = 1, 2), may be treated with stoichiometric amounts of water in the presence of a base, typically an amine such as triethylamine or pyridine, to capture resulting HC1 as a hydrochloride salt. After removal of the hydrochloride salt, a hydrolyzed silane, e.g. R⁵ _hSi(OH)i, can be isolated or used directly in solution when added to the reaction mixture of A' and B'.

[00116] In other embodiments, organosiloxane (C'i) (e.g. R⁵g(R⁶0)_fSiO(4_(_f+g))/2) and/or silane (C'ii) (e.g. R^SiZ- are treated with diluted aqueous acid, such as 0.1 N HC1, to form a mixture. The aqueous acid may be used in stoichiometric amounts relative to hydrolysable groups OR⁶ or Z' (e.g. wherein Z' = OR⁶). The mixture may be mixed or sonicated until two phases of aqueous acid and (C'i) and/or (C'ii) become one phase. A hydrolysis reaction can be monitored based on its exothermic nature. If necessary, the hydrolyzed organosiloxane and silane can be diluted with toluene and alcohol, such as ethanol or butanol, to maintain a uniform one-phase solution before being added to the reaction mixture of A' and B'.

[00117] In other embodiments, a solution of silane R⁵ _hSiZ'i (wherein Z' = CI and i = 1, 2), in diethylether (1:5) is added drop wise to a stirred cooled solution of stoichiometric amounts of triethylamine or pyridine and water in a diethylether- acetone mixture (e.g. 7: 1). The mixture may then be stirred for additional time and precipitated amine or pyridine hydrochloride may be filtered off and the filtrate reduced to 1/10 volume, e.g. using a rotary evaporator at 80°C and 15 mm Hg. An excess of pentane or other suitable hydrocarbon may be added to precipitate any residual amine or pyridine hydrochloride followed by filtering and volume reduction. A resulting solid may then be collected via filtration and washed with cold pentane or hydrocarbon and re-crystallized from pentane/diethylether. The product may be isolated as white solid. [00118] (C'i), which may be reacted to form the hydrolysis product, may be an organosiloxane having an average siloxane unit formula (II)

(f+g))/2_> and/or (C'ii) may be a silane having a general formula (III) R^SiZ'j. In these formulas, each R⁵ is hydrogen or a hydrocarbyl group, each R6 is typically an independently selected hydrogen atom or alkyl group having from 1 to 6 carbon atoms, aryl group having from 6 to 8 carbon atoms, or a polyether group having a general formula (VI) -(R^OijR^, where j is a value from 1 to 4, each R^ is an independently selected divalent alkylene group having from 2 to 6 carbon atoms, R^ is an independently selected hydrogen atom or monovalent alkyl group having from 1 to 6 carbon atoms, and the subscripts f and g are each independently any values from 0 to 3, wherein 0<f+g< 3.

[00119] In Formula (II), subscript f may be a value from 0.1 to 3 and alternatively from 1 to 3. In Formula (II), subscript g may be a value from 0.5 to 3 and alternatively from 1.5 to 2.5. In Formula (II), subscripts (f+g) may have a value from 0.6 to 3.9 and alternatively from 1.5 to 3. For example, f may be from 0.1 to 3 and g may be from 0.5 to 3. Examples of (C'i) described by Formula (II) include oligomeric and polymeric organosiloxanes, such as MQ resins.

[00120] Alternatively, Z' may be a hydrolysable group such as acetoxy, oxime, silazane, CI or OR^ and/or each R^ may be an independently selected hydrogen atom, alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 18 carbon atoms, aryl group having from 6 to 12 carbon atoms, epoxy group, amino group, or carbinol group. In one embodiment, at least one R5 groups of (C'i) and/or (C'ii) silane is an R group, as described above. Alternatively, at least one R5 = R may be as described by formula (II) or (III). Additionally, h is typically a value from 0 to 3, i is typically a value from 1 to 4 and (h+i) equals 4. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00121] The alkyl groups having 1 to 18 carbon atoms of R^ in Formulas (II) and

(III) are typically as described above for R1- Alternatively, the alkyl group may include 1 to 6 carbon atoms and be, for example, a methyl, ethyl, propyl, butyl, or hexyl group. The alkenyl groups having from 2 to 18 carbon atoms of R^ in Formulas (II) and (III) may be, for example, vinyl, propenyl, butenyl, pentenyl, hexenyl, or octenyl groups. Alternatively, the alkenyl group may include 2 to 8 carbon atoms and be, for example, a vinyl, allyl, or hexenyl group. The aryl groups having 6 to 12 carbon atoms of in formulas (II) and (III) may be phenyl, naphthyl, benzyl, tolyl, xylyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups. Alternatively, the aryl group may include 6 to 8 carbon atoms and be, for example, a phenyl group. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00122] In Formula (III), each Z' may be a chloro atom (CI) or OR* , where R6 is as described above. Alternatively, Z' may be OR^. In Formula (III), subscript h may be a value from 0 to 3, from 1 to 3, or from 2 to 3. In Formula (III), subscript i is a value from 1 to 4, from 1 to 3, or from 1 to 2. In Formula (III), subscripts (h+i) may equal 4. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated.

[00123] Examples of the silanes (C'ii), which may be reacted to form the hydrolysis product, described by Formula (III) include methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, phenylmethyldichlorosilane, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, and combinations thereof.

[00124] Typically, an amount of (D) water is utilized (and/or reacted) with (Α') and optionally (Β') so that polyheterosiloxanes having at least two non-Si metal elements can be formed. Since water can also be incorporated via hydrated metal salts (Ε 2), hydrated metal salts may be utilized such that no liquid water may be utilized and the water originates from the hydrated metal salts. 0.5 mole of water may be used for hydrolysis and condensation of 1 mole of alkoxy and other hydrolyzable groups. Alternatively, the amount of water utilized may be from 50 to 200, 70 to 150, from 80 to 120, 60 to 190, 70 to 180, 80 to 170, 90 to 160, 100 to 150, 110 to 140, or 120 to 130, , of the theoretical amount of water necessary for complete hydrolysis and condensation of alkoxy and other hydrolyzable groups, as first described above. All values and ranges of values therebetween the aforementioned values and ranges are hereby expressly contemplated. [00125] Typically, the water is added slowly to (Α') and optionally (Β') in an attempt to ensure that the metal alkoxide does not react quickly with the water so as to form a precipitate. Alternatively, the water may be diluted with one or more solvents, such as those described above. Depending on the solvents used and when they are added, the water may also be added at one time or during one or more of the method steps. Other hydrolyzable groups that may be present and need to be hydrolyzed and condensed are any found on the components used, including, but not limited to, chloro.

[00126] Each of the components (Α'), optionally (Β'), and/or (C) may be liquid or solid and it is typical that they are pre-mixed or dispersed. Stirring one or more of the components (Α'), optionally (Β'), and/or (C) in a solvent may provide a homogenous dispersion. As used herein, the terminology "dispersion" describes that the molecules of the various components (Α'), (Β'), and/or (C) are homogenously distributed. A solvent may not be needed if one or more components (Α'), (Β'), and/or (C) can be dispersed in one or more of each other. Such solvents may be as described and may be polar solvents, non-polar solvents, hydrocarbon solvents including aromatic and saturated hydrocarbons, alcohols, etc. Non-limiting examples of suitable solvents include hydrocarbonethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, methoxyethanol, methoxyethoxyethanol, butyl acetate, toluene, and xylene, alternatively isopropanol, 1-butanol, 2-butanol, and butyl acetate. The dispersing or mixing may be completed by any conventional means such as stirring.

[00127] Typically, reaction of (Α') and optionally (Β') with (D) water proceeds at room temperature (e.g. 20-30°C) but if desired, elevated temperatures up to about

140°C may be used. Alternatively, the temperature can range from 20°C to 120°C. Typically, the reaction may proceed from 30 minutes to 24 hours and alternatively from 10 minutes to 4 hours.

[00128] An optional method step includes removing the solvent to form the composition. The solvent can be removed by any conventional manner such as heating to elevated temperatures or using reduced pressure. The composition can then be redispersed in a solvent of choice such as toluene, THF, butyl acetate, chloroform, dioxane, 1-butanol, and pyridine. Since the Si-O-M may be susceptible to hydrolytic cleavage in the presence of water, to maximize shelf life it is typical to minimize the exposure of the composition to moisture. [00129] The method may also include the step of combining the (I) polyheterosiloxane composition and the (II) curable silicone. The polyheterosiloxane can be added to the curable silicone or vice versa. In one embodiment, the polyheterosiloxane is present in a solvent and this combination is added to the curable silicone, or vice versa. Alternatively, the polyheterosiloxane composition (and optionally the solvent) may be added to an "A" portion, a "B" portion, or both "A" and "B" portions, of the curable silicone, or vice versa. The polyheterosiloxane composition can also be added to the curable silicone after "A" and "B" portions are already themselves combined. Alternatively, the polyheterosiloxane composition can be added to the curable silicone, or vice versa, even if the curable silicone does not have "A" and "B" portions and is, instead, a single portion.

[00130] This disclosure also provides a cured silicone composition. Said differently, the cured silicone composition is the cured product of the aforementioned silicone composition including the (I) polyheterosiloxane composition and the (II) curable silicone wherein the curable silicone is cured by one or more of the aforementioned curing mechanisms. The cured silicone composition is not particularly limited and may be partially cured or completely cured. The cured silicone composition may be in any three dimensional form including a film, sheet, as a gel, as a molded form, as a cast form, etc. The level of clarity of the cured silicone composition may be predetermined by selecting and customizing the polyheterosiloxane composition and the curable silicone, as well as the methodology and conditions used to prepare the cured silicone composition.

[00131] This disclosure also provides an article which is not particularly limited and may be any three dimensional article. The article includes a substrate and a coating disposed on the substrate. The substrate is not particularly limited and may be a solid, liquid, or gel. In various embodiments, the substrate, in whole or in part, includes or is paper, plastic, a polymer, metal, wood, glass, or combinations thereof.

[00132] In one embodiment, the article is a molded article, e.g. with an overall shape or cross-section profile defined by a negative of the shape of a mold. In a non-limiting example, a mold having the shape of a hemi-spherical bowl may be utilized to produce an article having a shape of a spherical dome. Additionally, fine features or a pattern may be imparted onto the article, e.g. by utilizing a negative pattern in the mold such that vias would become pads, and vice versa. Molding techniques may include, but are not limited to, injection molding, overmolding, compression molding, casting, and imprint lithography. Feature size in any dimension may be greater than 5 nm, greater than 100 nm, greater than 1 μιη, or greater than 10 um.

[00133] The coating may be disposed on and in direct contact with the substrate or disposed on and separated in space with the substrate. The coating may be disposed on one or more portions of the substrate or on the entire substrate. The coating includes the cured silicone composition, e.g. the cured polyheterosiloxane composition including the (II) curable silicone described above. In various embodiments, the coating has an average thickness of from 1 to 10, 2 to 9, 3 to 8, 4 to 7, or 5 to 6, μιη or cm. In other embodiments, the coating has an average thickness of from 10 to 100, 15 to 95, 20 to 90, 25 to 85, 30 to 80, 35 to 75, 40 to 70, 45 to 65, 50 to 60, or about 65, μιη. In still other embodiments, the coating has an average thickness of from 100 to 1000, 150 to 950, 200 to 900, 250 to 850, 300 to 800, 350 to 750, 400 to 700, 450 to 650, 500 to 600, or about 650, μιη. In additional embodiments, the coating has an average thickness of from 1000 to 10000, 1500 to 9500, 2000 to 9000, 2500 to 8500, 3000 to 8000, 3500 to 7500, 4000 to 7000, 4500 to 6500, 5000 to 6000, or about 6500, μιη. In further embodiments, the coating has an average thickness of from 10000 to 100000, 15000 to 95000, 20000 to 90000, 25000 to 85000, 30000 to 80000, 35000 to 75000, 40000 to 70000, 45000 to 65000, 50000 to 60000, or about 65000, μιη. However, the coating is not limited to this thickness.

[00134] The coating may be disposed over a large area, on the substrate which may be rigid or flexible as recognized by those skilled in the art. The coating may also be described as a film. Non-limiting examples of coatings include bar coatings, Meyer bar coatings, gravure coatings, doctor blade coatings, slot-die coatings, spray coatings, spin coating castings, etc. The coating may be disposed on one or more portions of the substrate, or across an entirety of the substrate. The area coated may be larger than 1 mm in width or length, greater than 1 cm in width or length, greater than 20 cm in width or length, greater than 50 cm in width or length, or greater than 1 m in width or length. The coating may be disposed in such a way as to form a pattern. Methods used to form the coating include, but are not limited to, casting, ink jet printing, screen printing, stencil printing.

Additional Embodiments: [00135] In one additional embodiment, the silicone composition includes (I) polyheterosiloxane composition including the (A) first metal (Ml), the (B) second metal (M2), the (C) siloxy units having the formula (R^SiOm), (R^SiO^), (R¹Si0_{3 2}), and/or (Si0_4/2), wherein each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms, wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹3Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si03/2]t[Si0₄/2]_q, wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9, wherein m, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1, wherein one of (Ml) and (M2) is a lanthanide metal and the other of (Ml) and (M2) is a non-lanthanide metal chosen from aluminum (Al), zirconium (Zr), and combinations thereof, and the (II) the curable silicone. The silicone composition and/or the (I) polyheterosiloxane composition may also include an (E) photosensitizer. The (E) photosensitizer may be present in an amount of less than 3 moles of photosensitizer per one mole of the lanthanide metal, wherein the photosensitizer may imparts a larger peak emission intensity to the silicone composition and/or (I) polyheterosiloxane composition at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 to 470, 340 to 460, 350 to 450, 360 to 440, 370 to 430, 380 to 420, 390 to 410, or about 400, nm, as compared to a control silicone composition and/or polyheterosiloxane composition free of the photosensitizer. In other embodiments, the lanthanide metal is chosen from Ce, Eu, Nd, Er, Sm, Dy, Tb, and combinations thereof. Alternatively, the non-lanthanide metal may be aluminum or zirconium.

[00136] In other embodiments, the method of forming the silicone composition includes the step of reacting the (Α') metal (M3) alkoxide, the (Β ') optional hydrolyzable metal (M4) salt, the (C) hydrolysis product of at least one of: the (C'l) organosiloxane, the (C'2) silane, and combinations thereof, and the (E) amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β') to form the (I) polyheterosiloxane composition, wherein one of (M3) and (M4) is a lanthanide metal and the other of (M3) and (M4) is a non-lanthanide metal chosen from aluminum (Al), zirconium (Zr), and combinations thereof. The method may also include the step of introducing the (I) polyheterosiloxane composition to the (II) curable silicone or vice versa. [00137] This embodiment of the method, or any embodiment described above, may also include the step of introducing the (E) photosensitizer to one or more of (Α'), (Β'), (C), and (D) prior to the step of reacting and/or introducing (E). Just as above, the (E) photosensitizer may be present in the polyheterosiloxane composition in an amount of less than 3 moles of (E) photosensitizer per one mole of the lanthanide metal, and wherein the (E) photosensitizer may impart a larger peak emission intensity to the sensitized polyheterosiloxane composition at an excitation wavelength of from 200 to 1,000, 300 to 900, 400 to 800, 500 to 700, 600 to 700, 350 to 450, 320 to 480, 330 to 470, 340 to 460, 350 to 450, 360 to 440, 370 to 430, 380 to 420, 390 to 410, or about 400, nm, as compared to a control polyheterosiloxane composition free of the (E) photosensitizer.

[00138] In another embodiment, the method of forming the composition includes the step of reacting the (Α') metal (M3) alkoxide, the (Β') optional hydrolyzable metal (M4) salt, the (C) a silicon-containing material having silicon-bonded hydroxy groups, a (F) compatibilizing organosiloxane having at least one [R² ₃SiOi ₂] unit and having a weight average molecular weight (M_w) of less than 10,000 g/mol, and (D) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (Α') and optionally (Β').

[0002] In this embodiment, it is to be understood that (Α'), optionally (Β'), (C), (F), and (D) (and/or the (E) photosensitizer) may react together in any order. For example, (Α'), optionally (Β'), (C), (F) and (D) may react individually or with more of each other batch wise (e.g. simultaneously) and/or sequentially. One or more portions of (Α'), optionally (Β'), (C), (E), (F) and/or (D) may react individually or with more of portions of each other batch wise (e.g. simultaneously) and/or sequentially. (Β') may not be utilized and alkoxides may be utilized in the absence of a hydrolyzable metal. In another embodiment, (Β') is utilized, e.g. with an alkoxide.

[00139] Referring to the (F) compatibilizing organosiloxane, this organosiloxane has at least one [R² ₃SiOi ₂] unit. However, the compatibilizing organosiloxane may have more than one [R^SiOm] unit. The compatibilizing organosiloxane also has a weight average molecular weight (M_w) of less than 10,000 g/mol. In various embodiments, the M_w is less than 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000, or 500, g/mol. Alternatively, the M_w may be any value or range of values described immediately above or between those values described immediately above.

[00140] In one embodiment, the (F) compatibilizing organosiloxane has an average formula chosen from:

FD (RO)(C6H5)2SiCH2CH₂[(CH₃)2SiO]nOSi(CH₃)2(CH2)3CH₃;

HI) (R'0)(C6H5)2SiCH₂CH2 Si(CH₃)(OSi(CH₃)₃)2;

ΠΙΙ) (R'0)₃SiO(CH₃)2Si[(CH₃)2SiO]_mOSi(CH₃)2 (CHCH₂); or FIV) (R'0)(C₆H5)2SiOSi(CH₃)2CH2CH₂Si(CH₃)(OSi(CH₃)₃)2, wherein each n is independently from 3 to 100, alternatively from 10 to 12, each m is independently from 3 to 100, alternatively from 20 to 30, and R' is a Ci to C₄ alkyl group. Alternatively, the (F) compatibilizing organosiloxane may have the average formula:

wherein n is from 3 to 100, 3 to 50, or 3 to 15.

Alternatively, the (F) compatibilizin organosiloxane may have the average formula:

Even further, the (F) compatibilizing organosiloxane may have the average formula:

wherein n is from 3 to 100, alternatively from 20 to 30.

[00141] In other embodiments, the (F) compatibilizing organosiloxane has the formula: (Me^iO^MeSiCHzCHzS CH^OS CeHsMOMe). Even further, the (F) compatibilizing organosiloxane may have the formula (R⁸3SiO)_n(R⁸)(3-_n)Si-R⁹-Si(R⁸)2

OSi(R 1^l0^u)₂X, wherein n is 1 or 2. Each R 8 may be independently a monovalent Ci to C₂o hydrocarbyl. The hydrocarbyl group may independently be an alkyl, aryl, or alkylaryl group, including halogen substituted hydrocarbyls. Each R⁸ may independently be a Ci to C20 alkyl group, a Ci to Cis alkyl group, a Ci to C₆ alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. R⁸ may be an aryl group, such as phenyl, naphthyl, or an anthryl group, or any combination thereof. Alternatively, each R⁸ may independently be phenyl, methyl, or a combination of both. Each R⁹ may independently be a divalent hydrocarbon group including 2 to 12 carbon atoms or 2 to 6 carbon atoms and may be described as ethylene, propylene, or isobutylene. Each R¹⁰ may independently be a monovalent Ci to C30 hydrocarbyl including at least one aryl group, an aryl group, such as phenyl, naphthyl, or an anthryl group, any combination of the aforementioned alkyl or aryl groups, or phenyl (C₆H₅). X may be a hydrolyzable group chosen from -OR¹¹, CI, -OC(0)R⁹, -N(R⁹)₂, or wherein each R¹¹ is independently hydrogen or a Ci to C₆ alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, pentyl, or hexyl group. Alternatively, X may be an alkoxy, hydroxyl, carboxy, amine, chloride, or oxime group, e.g. -OCH₃, -OCH2CH₃, -OH, -CI, or -OC(=0)CH₃. In one embodiment, the organosiloxane has the following formula: (Me₃SiO)₂(Me)SiCH₂CH₂Si

wherein Me is a methyl group. Alternatively, the organosiloxane has the formula (R⁸ ₃SiO)_n(R⁸)(3__n)Si-G-Si(R⁸)2OSi(R¹⁰)₂X, wherein n is 1 or 2, R⁸ is independently a monovalent Ci to C2₀ hydrocarbyl, G is a siloxane or polysiloxane bridging group comprising at least one siloxy unit selected from a (R¹²2Si02a), (R¹²Si032), or (S1O42) siloxy units, wherein R¹² may be any organic group, R¹⁰ is independently a monovalent Ci to C₃₀ hydrocarbyl including at least one aryl group, X is a hydrolyzable group chosen from -OR⁹, CI, -OC(0)R⁹, -N(R⁹)₂, or -ON=CR⁹ ₂ and R¹¹ is hydrogen or a Ci to C₆ alkyl group. G may also be a combination of hydrocarbyl bridging groups, such as the divalent C2 to C₁₂ hydrocarbyl groups described above, and a siloxane or polysiloxane. In various embodiments, G is a polydimethylsiloxane of the formula - 0(Me2Si022)_q- where the subscript q is from 1 to 20, alternatively from 1 to 10, or alternatively from 1 to 5. When the polysiloxane bridging group includes a (R¹²Si032), or (S1O4_/2) siloxy unit(s), the group may further include additional M siloxy units to provide endcapping groups. Alternatively, one or more T or Q units may be silanol terminated.

[00142] Additional related embodiments include, but are not limited to, a silicone composition that includes the sensitized polyheterosiloxane composition as described immediately above and a silicone fluid. In another embodiment, the polyheterosiloxane composition is formed from the method described immediately above. In still another embodiment, the disclosure provides an article including a substrate and a coating disposed on the substrate, wherein the coating includes the cured product of the silicone composition, e.g. as described above.

EXAMPLES

[00143] The following examples are included to demonstrate various embodiments of the disclosure and are not limiting. All percentages are in weight % unless indicated otherwise. All measurements are conducted at 23°C unless indicated otherwise.

Photoluminescence

[00144] Photoluminescence of the examples may be measured using a Fluorolog-2 spectrofluorometer, manufactured by Jobin Yvon SPEX, and an Ocean Optics USB4000 spectrometer fiber coupled to an integrating sphere and using Ocean Optics' Spectra Suite software. The specific parameters are as described above.

Example 1 (Si+Ti+Eu)

[00145] 1.50g europium acetate hydrate, 21.3g titanium tetraisopropoxide, and 18.9g of IPA are charged into a 500 mL 3-neck flask and stirred at RT for 30 minutes. 1.26g H₂0 (4% in IPA) is added to the flask slowly. The reaction stirs for another 30 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 6.22g phenylmethyldimethoxysilane, 2.50g phenyltrimethoxysilane, 12.5g toluene and 2.34g 0.1N HQ and sonicating the combination for a total of 15 minutes. 37.5g of toluene is added to the europium/titanium reaction combination immediately followed by the pre-hydrolyzed siloxane solution. A total amount of H₂0 is -106%. Stirring is continued for 4 hours. Solvents are removed using a rotary evaporator at 57°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.6Euo.o3D^PhMeo.₂7T^Pho.i, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength of about 615 nm and a peak excitation wavelength of about 395 nm. In a 20 wt % solution in toluene the product shows approximately 11% quantum yield (QY). A TEM image of a representative sample of this example is shown in Figure 2. The TEM does not show any detectable particles at this resolution. The white spots represent signal noise.

Example 2 (Si+Ti+Yb)

[00146] 6.43g ytterbium acetate tetrahydrate, 67.8g titanium tetraisopropoxide, and 45g IPA are charged into a 500 ml 3-neck flask and stirred at RT for 30 minutes. 4.02g H₂0 (4% in IPA) is added into the flask slowly. 84g toluene is then added and stirred at RT for 60 minutes. A prehydrolyzed siloxane solution is prepared by mixing 30.7g phenylmethyldimethoxysilane, 25 g toluene, and 7.32g 0.01M HCl and sonicating the combination for 5 minutes. The prehydrolyzed siloxane solution is added to the flask quickly. A total amount of H₂0 is -100%. Stirring is continued at RT for 3 hours. Solvents are removed using a rotary evaporator at 60°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Ybo.o₃Tio.57D^PhMeo.4o, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

Example 3 (Si+Ti+Nd)

[00147] 4.37g neodymium acetate hydrate, 59.8g titanium tetraisopropoxide, and 40g IPA are charged into a 1 L3-neck flask and stirred at RT for 30 minutes. 4.35g H₂0 (4.5% in IPA) is added into the flask slowly. lOg IPA is then added and stirred at RT for 60 minutes. A prehydrolyzed siloxane solution is prepared by mixing 26.88g phenylmethyldimethoxysilane, 43 g toluene, and 6.43g 0.01M HCl and sonicating the combination for 15 minutes. The prehydrolyzed siloxane solution is added to the flask quickly. A total amount of H₂0 is -100%. 113 g toluene is then added and stirring is continued at RT for 3 hours. 300g solvents is distilled off and residual solvents are removed using a rotary evaporator at 60°C and 5 mm Hg. The product is a purple solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Ndo.o3Tio.57D^PhMeo.4o, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

Example 4 (Si+Ti+Dy)

[00148] 4.75g dysprosium acetate tetrahydrate, 62.4g titanium tetraisopropoxide, and 41.0 IPA are charged into a 1 L 3-neck flask and stirred at RT for 30 minutes. 4.00g H₂0 (4% in IPA) is added into the flask slowly. Then added 65g toluene and stirred at RT for 60 minutes. A prehydrolyzed siloxane solution is prepared by mixing 28.2g phenylmethyldimethoxysilane, 55 g toluene, lOg IPA, and 6.72g 0.01M HCl and sonicating the combination for 15 minutes. The prehydrolyzed siloxane solution is added to the flask quickly. A total amount of H₂0 is -100%. Stirring is continued at RT for 3.5 hours. Solvents are removed using a rotary evaporator at 60°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Dyo.o₃Tio.57D^PhMeo.4o, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform. The product shows yellow luminance with blue and near UV excitation, with a peak emission wavelength of about 595 nm and a peak excitation wavelength of about 390 nm.

Example 5 (Si+Ti+Sm)

[00149] 5.33g samarium acetate hydrate, 72.0g titanium tetraisopropoxide, and 47.6g IPA are charged into a 1 L 3-neck flask and stirred at RT for 30 minutes. 4.55g H₂0 (4% in IPA) is added into the flask slowly. Then 132g toluene is added and stirred at RT for 60 minutes. A prehydrolyzed siloxane solution is prepared by mixing 28.83g phenylmethyldimethoxysilane, 4.12g phenyltrimethoxysilane, 25 g toluene, and 8.0g 0.01M HCl and sonicating the combination for 15 minutes. The prehydrolyzed siloxane solution is added to the flask quickly. A total amount of H₂0 is -100%. Stirring is continued at RT for 4 hours. Solvents are removed using a rotary evaporator at 60°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Smo.o3Tio.57D^PhMeo.35T^Pho.o5, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform. The product shows yellow luminance with blue and near UV excitation, with a peak emission wavelengths of about 570 nm, 600 nm and 650 nm, and a peak excitation wavelength of about 400 nm. In a 20 wt % solution in toluene the product shows approximately 0.2% quantum yield (QY).

Example 6 (Si+Ti+Tb

[00150] 5.53g terbium acetate hydrate, 73.2g titanium tetraisopropoxide, 32g toluene, and 41.0 IPA are charged into a 1 L 3-neck flask and stirred at RT for 30 minutes. 4.65g H₂0 (4% in IPA) is added into the flask slowly. Then 69g toluene is added and stirred at RT for 60 minutes. A prehydrolyzed siloxane solution is prepared by mixing 32.85g phenylmethyldimethoxysilane, 25 g toluene, and 7.90g 0.01M HQ and sonicating the combination for 15 minutes. The prehydrolyzed siloxane solution is added to the flask quickly. A total amount of H₂0 is - 100%. Stirring is continued at RT for 3.5 hours. Solvents are removed using a rotary evaporator at 60°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tbo.o₃Tio.57D^PhMeo.4o, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform. The product shows green luminance with blue and near UV excitation, with a peak emission wavelength of about 545 nm and a peak excitation wavelength of about 485 nm. In a 20 wt % solution in toluene the product shows approximately 0.1% quantum yield (QY).

Example 7 (Si+Ti+Er)

[00151] 1.25g erbium acetate hydrate, 17.05g titanium tetraisopropoxide, 30g toluene, and 15.2g IPA are charged into a 250ml 3-neck flask and stirred at RT for 30 minutes. l .OOg H₂0 (4% in IPA) is added into the flask slowly. A prehydrolyzed siloxane solution is prepared by mixing 4.92g phenylmethyldimethoxysilane, 1.98g phenyltrimethoxysilane, 10.0 g toluene, and 1.81g 0.1M HQ and sonicating the combination for 15 minutes. The prehydrolyzed siloxane solution is added to the flask quickly. A total amount of H₂0 is -110%. Stirring is continued at RT for 4 hours. Solvents are removed using a rotary evaporator at 60°C and 5 mm Hg. The product is a pink solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Ero.o3Tio.6oD^PhMe o.₂7T^Ph o.io, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

Example 8 (Si+Al+Eu)

[00152] 31. lg aluminum sec-butoxide stock solution (2.50 mmol/g in 2-butanol), 15.0 g 2-butanol, and 50.0 g toluene are mixed in a 250ml 3-neck flask. Under stirring, 9.0 g 39% Ph₂MeSiOH heptane solution is added into the flask. The clear solution is stirred at RT for 30 minutes. 5.85g europium acetate hydrate is added to the flask and the solution is heated to 90°C for 100 minutes to form a clear yellow solution. A prehydrolyzed siloxane solution is prepared by mixing 6.75g phenylmethyldimethoxysilane, 1.99g phenyltrimethoxysilane, and 1.88g 0.01M HQ and sonicating the combination for 20 minutes. The prehydrolyzed siloxane solution is added to the flask and the solution turns colorless quickly. After 10 minutes, 0.34g H₂0 (10% in 2-butanol) is added to the flask. A total amount of H₂0 is -100%. Stirring is continued at 90°C for 2 hours. ~75g solvent is distilled off and the solution is cooled to ~70°C. Solvent residue is removed using a rotary evaporator at 70°C and 10 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Euo.ioAlo.4oM^Ph2Meo.ioD^PhMeo.₂4T^Pho.o6, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform. The product shows orange or red luminance with blue and near UV excitation, with a peak emission wavelength of about 615 nm and a peak excitation wavelength of about 395 nm.

Example 9 (Si+Zr+Eu

[00153] 5.07g europium acetate hydrate, 17.65g NBZ solution (80% zirconium tetrabutoxide+20% 1-butanol), and 40g toluene are charged into a 250 ml 3-neck flask and refluxed at 107°C for 80 minutes. A prehydrolyzed siloxane solution is prepared by mixing 2.99g phenylmethyldimethoxysilane, 1.80g phenyltrimethoxysilane, 10 g toluene, 4g butanol, and 0.86g 0.1N HC1 and sonicating the combination for 30 minutes. The prehydrolyzed siloxane solution is added to the flask and the solution is continued refluxing for 30 minutes. Then a solution including 0.66g H₂0 and 13g butanol is added into the flask. A total amount of H₂0 is -100%. The solution is maintained at refluxing temperature for 30 minutes. Solvent is removed using a rotary evaporator at 85°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Euo.₂oZro.5oD^PhMeo.₂₂sT^Pho.o75, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform. In a 10wt% solution in butyl acetate the product shows approximately 31% quantum yield (QY).

Example 10 (Si+Ti+Eu

[00154] 1.407 g of europium undecylenate hydrate (prepared by the experimental procedure disclosed in Eur. J. Inorg. Chem. 2000, 1429 - 1436 for the synthesis of lanthanide dodecanoates), 2.737 g of titanium n-butoxide, and 4 g of 1-propanol are charged into a 125 mL Erlenmeyer flask equipped with reflux condenser and stirs at 60 - 70 °C until all compounds dissolve. 0.145 g of water dissolved in 1 g of 1- propanol is added and the solution stirs for 30 min. A pre-hydrolyzed siloxane solution is prepared by mixing 1.373 g of phenylmethyldimethoxysilane, 0.494 g of phenyltrimethoxysilane, 5g toluene and 0.377 g 0.1N HCl and stirring the combination rapidly for a total of 5 min. The pre-hydrolyzed siloxane solution is added and the solution stirs at 60°C for 4 hours. A total amount of H₂0 is -110%. Solvents are removed first using a rotary evaporation at 80°C and 15 mm Hg, then using high vacuum at 0.05 mm Hg and 80°C. The product is a yellow-orange viscous liquid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.4Eu₀.iD^PhMeo.375T^Pho.i25, soluble in many organic solvents such as toluene, THF, and chloroform. This product exhibits orange or red luminance with blue and near UV excitation, with a peak emission wavelength of 615 nm and a peak excitation wavelength of 395 nm. In a 20 wt % solution in toluene the product had a 13.6 % quantum yield.

Examples 11-27

[00155] A variety of additional compositions are synthesized using similar synthetic procedures as described above. For Examples 11-27 below, the lanthanide ion luminescent center is Eu, with red/orange luminance with blue and UV excitation. The peak emission wavelength is approximately 615 nm, and the peak excitation wavelength is approximately 395 nm.

TABLE 1

Example 28 (Si+Ti+Zn+Eu)

[00156] 3.50g europium acetate hydrate, 1.73g zinc acetate hydrate, 16.2g titanium n- butoxide, and 20g of toluene are charged into a 500 mL 3-neck flask and stirred at 60°C for 30 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 3.45g phenylmethyldimethoxysilane, 1.89g phenyltrimethoxysilane, 15g toluene and 1.85g 0.1N HCl and sonicating the mixture for a total of 30 minutes. The solution is stirred at 60°C for 4 hours after the addition of pre-hydrolyzed siloxane solution. A total amount of H₂0 is -110%. Solvents are removed using a rotary evaporation at 80°C and 5 mm Hg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.5Zno.iEuo.iD^PhMeo.₂T^Pho.i, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. In a 20 wt % solution in toluene the product shows approximately 27% quantum yield (QY).

Example 29 (Si+Ti+Al+Zn+Eu)

[00157] 3.11g europium acetate hydrate, 1.64g zinc acetate hydrate, 6.10g titanium n- butoxide, 2.22g aluminum sec -butoxide, 1.91g diphenylmethylmethoxysilane, and 30g of toluene are charged into a 500 mL 3-neck flask and stirred at refluxing temperature (about 105°C) for 120 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 2.45g phenylmethyldimethoxysilane, 2.68g phenyltrimethoxysilane, 15g toluene and 0.85g 0.1N HCl and sonicating the mixture for a total of 30 minutes. Then this pre-hydrolyzed siloxane solution is added into the flask drop-wise. 10.9g 4% water in n-butanol solution is also added drop-wise. The solution is stirred at refluxing temperature for another 60 minutes before removing the solvents using a rotary evaporation at 80°C and 5 mm Hg. A total amount of H₂0 is -110%. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.2Alo.2Zno.iEuo.iD^PhMeo.i5T^Pho.i5M^Ph2Meo.i, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. In a 2wt % solution in toluene the product shows approximately 15% quantum yield (QY).

Example 30 (Si+Ti+Y+Eu

[00158] 1.787g europium acetate hydrate, 3.505g titanium n-butoxide, 1.541g yttrium butoxide, and 17g of toluene plus 8g butanol are charged into a 500 mL 3 -neck flask and stirred at 70°C for 120 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 0.699g phenylmethyldimethoxysilane, 0.276g phenyltrimethoxysilane, 5g toluene and 0.423g 0.1N HC1 and sonicating the mixture for a total of 30 minutes. Then this pre-hydrolyzed siloxane solution is added into the flask drop-wise. 3.245g of 5% water in n-butanol solution is also added drop- wise. The solution is stirred at room temperature for another 120 minutes before removing the solvents using a rotary evaporation at 65 °C and 1 mbar. A total amount of H₂0 is -110%. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.55Yo.o5Euo.₂D^PhMeo.i5T^Pho.o5, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. In a 2wt % solution in toluene the product shows approximately 51% quantum yield (QY).

Example 31 (Si+Ti+Mn+Eu)

[00159] 1.896g europium acetate hydrate, 0.134g manganese acetate hydrate, 5.394g titanium n-butoxide, and 30g of toluene plus lOg n-butanol are charged into a 500 mL 3-neck flask and stirred at 70°C) for 200 minutes. The solution turns yellow-orange. A pre-hydrolyzed siloxane solution is prepared by mixing 0.741g phenylmethyldimethoxysilane, 0.270g phenyltrimethoxysilane, 5g toluene and 0.45 lg 0.1N HC1 and sonicating the mixture for a total of 30 minutes. Then this pre- hydrolyzed siloxane solution is added into the flask drop-wise. 2.881g of 5% water in n-butanol solution is also added drop- wise. The solution is stirred at room temperature for another 120 minutes before removing the solvents using a rotary evaporation at 65°C and 1 mbar. A total amount of H₂0 is -110%. The product is a grey solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tio.58Mno.o₂Euo.₂D^PhMeo.i5T^Pho.o5, soluble in many organic solvents such as toluene, THF, and chloroform. This product has improved absorption in the near UV to blue light (350-450nm). The peak emission wavelength is around 615 nm with approximately 2% quantum yield (QY) under 395nm excitation.

Example 32 (Si+Ti+Ag+Eu

[00160] 1.891g europium acetate hydrate, 0.038g silver neodecanoate, 5.508g titanium n-butoxide, and 30g of toluene plus lOg n-butanol are charged into a 500 mL 3-neck flask and stirred at 70°C for 90 minutes. The solution turns brown. A pre- hydrolyzed siloxane solution is prepared by mixing 0.757g phenylmethyldimethoxysilane, 0.273g phenyltrimethoxysilane, 5g toluene and 0.508g 0.1N HC1 and sonicating the mixture for a total of 30 minutes. Then this pre- hydrolyzed siloxane solution is added into the flask drop-wise. 2.965g of 5% water in n-butanol solution is also added drop- wise. The solution is stirred at room temperature for another 120 minutes before removing the solvents using a rotary evaporation at 65°C and 1 mbar. A total amount of H₂0 is -110%. The product is a grey solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tio.595Ago.oo5Eu₀.₂D^PhMeo.i5T^Pho.o5, soluble in many organic solvents such as toluene, THF, and chloroform. This composition is highly absorptive in the near UV and blue range (380-500nm). The peak emission wavelength is around 615 nm with approximately 25% quantum yield (QY) under 395nm excitation.

Example 33 (Si+Ti+La+Eu)

[00161] 1.880g europium acetate hydrate, 0.105g terbium acetate hydrate, 5.426g titanium n-butoxide, and 30g of toluene plus lOg n-butanol are charged into a 500 mL 3-neck flask and stirred at 70°C for 150 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 0.737g phenylmethyldimethoxysilane, 0.265g phenyltrimethoxysilane, 5g toluene and 0.470g 0.1N HC1 and sonicating the mixture for a total of 30 minutes. Then this pre-hydrolyzed siloxane solution is added into the flask drop-wise. 3.350g of 5% water in n-butanol solution is also added drop-wise. The solution is stirred at room temperature for another 120 minutes before removing the solvents using a rotary evaporation at 65 °C and 1 mbar. A total amount of H₂0 is -110%. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.598Lao.oiEuo.2D^PhMeo.i5T^Pho.o5, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. In a 2wt % solution in toluene the product shows approximately 70% quantum yield (QY).

Example 34 (Si+Ti+Gd+Eu

[00162] 1.809g europium acetate hydrate, 0.458g gadolinium acetate hydrate, 4.889g titanium n-butoxide, and 25g of toluene plus lOg n-butanol are charged into a 500 mL 3-neck flask and stirred at 70°C for 90 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 0.717g phenylmethyldimethoxysilane, 0.267g phenyltrimethoxysilane, 5g toluene and 0.346g 0.1N HC1 and sonicating the mixture for a total of 30 minutes. Then this pre-hydrolyzed siloxane solution is added into the flask drop-wise. 2.974g of 5% water in n-butanol solution is also added drop-wise. The solution is stirred at room temperature for another 120 minutes before removing the solvents using a rotary evaporation at 65 °C and 1 mbar. A total amount of H₂0 is -110%. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.55Gd₀.o5Euo_.2D^PhMeo.i5T^Pho.o5, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. In a 2wt % solution in toluene the product shows approximately 57% quantum yield (QY).

Example 35 (Si+Ti+Tb+Eu

[00163] 1.889g europium acetate hydrate, 0.020g terbium acetate hydrate, 5.551g titanium n-butoxide, and 30g of toluene plus 20g n-butanol are charged into a 500 mL 3-neck flask and stirred at 70°C for 90 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 0.745g phenylmethyldimethoxysilane, 0.278g phenyltrimethoxysilane, 5g toluene and 0.438g 0.1N HC1 and sonicating the mixture for a total of 30 minutes. Then this pre-hydrolyzed siloxane solution is added into the flask drop-wise. 4.079g of 5% water in n-butanol solution is also added drop-wise. The solution is stirred at room temperature for another 120 minutes before removing the solvents using a rotary evaporation at 65 °C and 1 mbar. A total amount of H₂0 is -110%. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.598^rTbo.oo2Euo.2D^PhMeo.i5T^Pho.o5, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. In a 2 wt % solution in toluene the product shows approximately 55% quantum yield (QY).

Example 36 (Si+Ti+Eu)

[00164] 1.372 g of europium isopropoxide (prepared according to a procedure published in U.S. Pat. No. 4,507,245 from anhydrous europium acetate and sodium isopropoxide) is added to 3.316 g of titanium isopropoxide in 40 ml of anhydrous toluene and 20 ml of anhydrous isopropanol. The solution is cooled down to 0-5 °C and 6.883 g of a resin is added. This resin has the formula M₀.43Q0.57 wherein M_n = 3230 g/mol and may be prepared according to techniques taught by Daudt in U.S. Pat. No. 2,676,182, which is expressly incorporated herein by reference relative to such techniques. The solution is heated to 80 °C for 1 hour after that it is cooled down to 0- 5 °C again and 0.509 g of water in 15 ml of isopropanol is added drop wise over 2 - 3 hours. The solution is warmed to ambient overnight and finally heated to 80 °C for 1 hour. A total amount of H₂0 is -100%. The clear solution is filtered through 0.2 μιη PTFE filter and solvents are removed first using a rotary evaporation at 80°C and 15 mm Hg, for 30 min. The product is a white powdery solid with a composition of Tio.7Euo.25MQ⁴⁰⁷ o.o5_> soluble in many organic solvents such as toluene, THF, and chloroform. The product shows orange or red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. The quantum yield of this Example is determined in an 8.4 wt% solution of the Example in toluene and is approximately 10% QY.

Example 37 (Si+Ti+Eu)

[00165] 1.365 g of europium isopropoxide is added to 3.535 g of titanium isopropoxide in 40 ml of anhydrous toluene and 20 ml of anhydrous isopropanol and the solution is cooled down to 0-5 °C. A pre-hydrolyzed siloxane solution is prepared by mixing 9.130 g of diphenylmethoxysilylethyl terminated polydimethylsiloxane, 20 ml of isopropanol and 0.693 g 0.1N HC1 and treating the mixture in the ultra sonic bath for a total of 30 min. The pre-hydrolyzed siloxane solution is drop wise added over 1 hour after that the solution is stirred at ambient overnight and then heated to 80 °C for 1 hour. A small amount of precipitate forms which is removed by centrifuge and filtering of the supernatant solution through a 0.45 μιη PTFE filter. The solvents are removed first using a rotary evaporation at 80°C and 15 mm Hg, for 30 min The product is a white powdery solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tio.5iEuo.i7M^Ph2o.32, soluble in many organic solvents such as toluene, THF, and chloroform. The product shows orange or red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm. The quantum yield of this Example is determined in an 8.4 wt solution of the Example in toluene and is approximately 13% QY.

Example 38 (Si+Ti+Eu

[00166] 1.372 g of europium isopropoxide is added to 2.961 g of titanium isopropoxide in 40 ml of anhydrous toluene and 20 ml of anhydrous isopropanol and the solution is cooled down to 0-5 °C. Then 1.014 g of diphenyldisilanol is added followed by drop wise addition of 0.310 g pre-hydrolyzed phenyltrimethoxysilane and 0.499 g 0.1N HC1 in 10 ml of isopropanol by treating the mixture in a ultra sonic bath for a total of 30 min. A total amount of H₂0 is -100%. The solution is allowed to warm up to ambient and stirred overnight and then heated to 80 °C for 1 hour. A small amount of precipitate forms which is removed by centrifuge and filtering of the supernatant solution through a 0.45 μιη PTFE filter. Solvents are removed first using a rotary evaporation at 80°C and 15 mm Hg. The product is a white powdery solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tio.5Euo.2D^Ph2o.₂25T^Pho.o75 soluble in many organic solvents such as toluene, THF, and chloroform. The product shows orange or red luminance with blue and near UV excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm The quantum yield of this Example is determined in an 8.4 wt% solution of the Example in toluene and is approximately 4% QY. Example 39 (Si+Zr+Tb)

[00167] 4.55g terbium acetate hydrate, 21.37g NBZ solution (80% zirconium tetrabutoxide and 20% 1-butanol), and 50g toluene are charged into a 250 ml 3-neck flask and refluxed at 107°C for 80 minutes. A prehydrolyzed siloxane solution is prepared by mixing 7.11g phenylmethyldimethoxysilane, 3.3 lg phenyltrimethoxysilane, 20 g toluene, 5g butanol, and 2.23g 0.1N HC1 and sonicating the combination for 30 minutes. The prehydrolyzed siloxane solution is added to the flask and the solution is continued refluxing for 30 minutes. The total amount of H₂0 is -110%. The solution is maintained at refluxing temperature for 30 minutes. Solvent is removed using a rotary evaporator at 75 °C and 1 mbar. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tbo_.ioZro.4oD^PhMeo.35T^Pho.i5, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform. This materials has several excitation peaks in the range of 310-380nm, and emit at 487, 543, 583 and 620nm. In a 5 wt% solution in toluene the product shows approximately 6% quantum yield (QY).

[00168] The aforementioned examples demonstrate that the composition of this disclosure has excellent solubility and quantum yield. In addition, the composition includes well dispersed metals because at least one oxygen atom of the siloxy units is bonded to at least one of (Ml) and/or (M2). The metals may bond with one another, further increasing the variety of the metals, and therefore the quality of the dispersion of the metals, in the composition. The metal allows the composition to be luminescent such that excitation and emission spectra can be manipulated and customized based on choice of metal.

Generic Synthesis of r(Ml)Lr(M2)lhrR¹.SiO_I^½rR¹ ₂Si0₂^l_iirR¹Si0^1₁:

[00169] 150 ml of a 2: 1 ratio of toluene and n-butanol is charged to a 3-neck 250 ml round flask equipped with reflux condenser and temperature probe. Titanium alkoxides are charged to the flask followed by zinc and europium salts listed in Table 1. A stoichiometric amount of water is added dissolved in 15 ml of a 3: 1 ratio n- butanol and toluene at room temperature (see Table 2). TABLE 2

[00170] The reaction mixture is stirred for 2 hours at 75 °C then the pre-hydrolyzed siloxane moieties are dissolved in 15 ml of a 3: 1 ratio n-butanol and toluene and are added (Table 3):

TABLE 3

[00171] The reaction mixture is stirred for further 2 hours at 75 °C, cooled to ambient temperature and then filtered through 0.45 μιη PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at 75 °C and 15 mmHg. The products are white solids with the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents (Table 4):

TABLE 4

[00172] 150 ml of a 7: 1 ratio of toluene and n-butanol is charged to a 3-neck 250 ml round flask equipped with reflux condenser and temperature probe. Europium ethyl hexanoate (Table 5) is added together with 1 mol equivalent of water and stirred for 15 min at ambient. Then the titanium alkoxides and the zinc salt are added as listed in Table 5.

TABLE 5

[00173] The reaction mixture is stirred for 1 hour at 90 °C, then the following siloxanes are dissolved in 15 ml of a 3: 1 ratio n-butanol and toluene and are added (Table 6): TABLE 6

[00174] The reaction mixture is stirred for further 2 hours at 90 °C, cooled to ambient and then filtered through 0.45 μιη PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at 75°C and 15 mmHg. The products are white solids with the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents (Table 7):

TABLE 7

Generic Synthesis of r MDlJ M^lhrR^SiO^^kfR SiO^^LrR^iO^,!,:

[00175] 150 ml of a 2: 1 ratio of toluene and n-butanol is charged to a 3-neck 250 ml round flask equipped with reflux condenser and temperature probe. Titanium n- butoxide is charged to the flask followed by zinc and europium salts. A stoichiometric amount of water is added dissolved in 15 ml of a 3: 1 ratio n-butanol and toluene added at room temperature (see Table 8).

TABLE 8

[00176] The reaction mixture is stirred for 2 hours at 75 °C then the pre-hydrolyzed siloxane moieties dissolved in 15 ml of a 3: 1 ratio n-butanol and toluene are added (table 9):

TABLE 9

[00177] The reaction mixture is stirred for further 2 hours at 75 °C, cooled to ambient and then filtered through 0.45 μιη PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at75°C and 15 mmHg. The products are white solids with the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents (Table 10): TABLE 10

Description of Preparation of Cured Silicone Compositions:

[00178] Samples of the aforementioned polyheterosiloxane compositions are dissolved 4 times their weight in a 4:1 mixture of toluene and IPA. Part B of Dow Corning^® OE-6630 A/B Kit or Dow Corning^® OE-6003 Optical Elastomer is added, mixed and solvents removed under vacuum at 80°C. Each of Dow Corning^® OE-6630 A/B Kit and Dow Corning^® OE-6003 are 2 part hydrosilylation curable compositions that are commercially available. After cooling, part A of OE 6630 or 6003 is added, mixed and degassed under vacuum. The combination of Parts A and B, together, or the OE-6003 Optical Elastomer, are examples of the (II) curable silicone of this disclosure.

[00179] The resulting mixture is poured into molds (0 25 mm, 2-4 mm deep) and cured for at least 1 h at 120 °C (resin + OE 6003) or 150 °C (resin + OE 6630). The cured sample is released from the mold and visually evaluated for clarity. More specifically, clarity is visually evaluated on a scale of 0 to 100 wherein 0 represents totally clear and 100 represents totally opaque.

[00180] In Table 11 below, "Clear" represents scale scores of approximately from 0- 10%, "Cloudy" represents scale scores of approximately from 11-30%, "Hazy" represents scale scores of approximately from 31-70%, and "Opaque" represents scale scores of approximately 71-100%. These scale scores are approximated based on visual approximation using haze standard plates (BYK Gardner, Columbia, MD, USA) as reference and/or Haze measurements according to ASTM D1003. TABLE 11

Example 54 - Hydrosilylation- Curable Silicone Composition:

[00181] 10.80g 10% Cerium 2-ethylhexanoate toluene solution is charged to a 250ml flask. 3.67g aluminum sec-butoxide/sec-butanol solution (2.5mmol Al/g) is then added to obtain a clear yellow solution after stirring at 90°C for 30 minutes. A prehydrolyzed siloxanes solution is then added. The prehydrolyzed siloxanes solution is prepared by mixing 20. lg (C), lO.Og octyltrimethoxysilane, 2.0g 0.1M HC1, 16.5g IPA, and 5.2g toluene and sonicating the mixture for 15 minutes. The clear solution is stirred at 90°C for 2.5 hours and solvents are removed using a rotary evaporator at 90°C and 8 mmHg. The product is a clear brown viscous liquid.

[00182] 0.81g of the material formed above is mixed with 9.1g 165DP polydimethylsiloxane, 0.23g 65DP methylhydrogensiloxane, and 1 drop of 6000 ppm Pt catalyst in a dental cup. After mixing, the mixture is cured in a glass dish at 120°C for 10 minutes to form a clear elastomeric article. Additional Examples Utilizin2 Non-Lanthanide Metal Polyheterosiloxanes Example 55 - Condensation-Curable Silicone Composition:

[00183] 14.50g ZnAc₂.2H₂0, 61.1 lg Titanium n-butoxide, 20g 1-BuOH, and 60g toluene are charged to a 1 liter flask. A clear solution is obtained after the mixture is stirred at RT for at least 2 hours. 34.45g Ph₂Si(OMe)₂ is added into the flask. Under stirring a solution containing 8.80g 0.1M HCl and 79.2g 1-BuOH is added into the flask slowly. After stirring at RT for 50 minutes, the solution is heated to 90°C for 15 minutes and turns translucent. Then the solution is cooled to ~40°C. A solution containing 0.79g 0.1M HCl and 7.1g 1-BuOH is added to the flask quickly. The total amount of H₂0 is 145%. The solution is heated to 90°C again for 28 minutes. Then -69 g solvent is distilled off. The solution is translucent after cooling to RT. Finally the solvents are removed using a rotary evaporator. The white solid has the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents: Tio.56Zno.i4D^Ph2o.3o. This solid is then dissolved in butyl acetate at 45wt%.

[00184] To 2.73g of the material above is added 1.71g of phenylmethylsiloxane polymer with silanol end groups (-100DP) to form the silicone composition. The mixture is applied by dropper onto clean glass slides 25 (1 cm x 1 cm cover slips). The silicone composition is then cured by heating at 70°C for one hour followed by 150°C for one hour in a forced air oven to obtain clear colorless coatings.

Example 56 - Condensation-Curable Silicone Composition:

[00185] 68.4g 4g Titanium n-butoxide, 21.0g 1-BuOH, 20.2g toluene, and 6.43g AgNC>3 are mixed in a 500ml flask. The mixture is stirred at RT for ~2 hours and then 43.2g of solution containing 10% 0.1N HCl in 1-BuOH are added thereto. The mixture is then stirred for 1.5 hours at RT. A prehydrolyzed siloxane solution is then added. The prehydrolyzed siloxane is prepared by mixing 28.50g dimethyldimethoxysilane and 8.60g 0.05N HNO₃ and sonicating the mixture for 10 minutes. After stirring at RT for 3 hours, the solution is filtered through a glass wool filled funnel to remove small amounts of precipitation. After addition of 144g toluene, -1/2 of the solvents is removed by a rotary evaporation apparatus. A dark brown solution is obtained and has the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents: Tio.4₂Ago.o8D^Me2o.5o · [00186] To 2.50g of the material above is added 2.00g of polydimethylsiloxane polymer with silanol end groups (-100DP, 40% solids in butyl acetate) to form the silicone composition. The mixture is applied by dropper onto clean glass slides (1 cm x 1 cm cover slips). The silicone composition is then cured by heating at 70°C for one hour followed by 150°C for one hour in a forced air oven to obtain dark brown coatings.

Example 57 - Condensation-Curable Silicone Composition:

[00187] 78.2g Titanium n-butoxide, 36.0g 1-BuOH, and 41.3g toluene are mixed in a 500ml flask. Under stirring a mixture containing 1.93g AgNC>3, 3.27g 0.1N HNO₃, and 29.43g 1-BuOH is added into the flask and stirred at RT for 50 minutes to form a dark brown solution. Then 9.98g ZnAc₂.2H₂0 and 12g toluene is added into the flask and the mixture is stirred at RT for 1 hour. A prehydrolyzed siloxane solution is then added. The prehydrolyzed siloxane solution is prepared by mixing 34. lg dimethyldimethoxysilane, 11. Og 0.05N HNO₃, and 20. Og toluene and sonicating the mixture for 10 minutes. After stirring at RT for 3 hours, the solution is filtered through a glass wool filled funnel to remove small amounts of precipitation. Solvents are removed by a rotary evaporation apparatus. The product is dissolved in butyl acetate at 40wt%. A dark brown solution is obtained and has the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents: Tio.4oAgo.o₂Zno.o8D^Me2o.5o ·

[00188] To 3.53g of the material above is added 2.00g of polydimethylsiloxane polymer with silanol end groups (-100DP, 40% solids in butyl acetate) to form the silicone composition. The mixture is applied by dropper onto clean glass slides (1 cm x 1 cm cover slips). The silicone composition is then cured by heating at 70°C for one hour followed by 150°C for one hour in a forced air oven to obtain brown coatings.

Example 58 - Condensation-Curable Silicone Composition:

[00189] 88.9g Titanium n-butoxide, 25.0g 1-BuOH, 50.0g toluene, and 14.20g ZnAc₂.2H₂0 are mixed in a 500ml flask and stirred overnight. 47. Og solution containing 10% 0.1N HC1 in 1-BuOH is added into the flask and stirred for 70 minutes at RT. A prehydrolyzed siloxane solution is then added. The prehydrolyzed solution is prepared by mixing 38.8g dimethyldimethoxysilane and 10.45g 0.02 N HC1 and sonicating the mixture for 10 minutes. After stirring at RT for 6 hours, solvents are removed by a rotary evaporation apparatus. The product is dissolved in butyl acetate at 48wt%. A clear solution is obtained that has the following mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents: Ti0.4oZno.ioD^Me2o.so-

[00190] To 3.00g of the material above is added 2.00g of polydimethylsiloxane polymer with silanol end groups (-100DP, 40% solids in butyl acetate) to form the silicone composition. The mixture is applied by dropper onto clean glass slides (1 cm x 1 cm cover slips). The silicone composition is then cured by heating at 70°C for one hour followed by 150°C for one hour in a forced air oven to obtain clear coatings.

Examples 59-62 - Condensation-Curable Silicone Compositions:

[00191] Solvent-borne formulations are mixed in glass vials on a mixing wheel at a moderate rotation rate. Typical castings of the coatings are done by dropper onto standard glass microscope slides. After drying at RT overnight, the coatings are cured at 150°C for 1-2 hours. Some formulations include hexamethyldisiloxane added to improve the wet-out and surface smoothness of the final coating. Table 12 below includes coating formulation details (based on 100% solids / actives content):

TABLE 12

In the aforementioned Examples, the "BA" is butyl acetate, and "Tol" is toluene.

[00192] Haze is visually indicative of phase separation of the polyheterosiloxane and the curable silicone, when in solution together. Typically, optical applications utilize clear materials with as minimal amounts of haze as possible. The data set forth above throughout the Examples demonstrates that this invention effectively forms articles with minimal haze. In addition, the polyheterosiloxane composition of this invention typically can be utilized in products in higher concentration than traditional phosphors without the products suffering from haze, phase segregation, agglomeration or settling of particles thereby allowing consistent products to be formed. Additionally, other functionalities imparted by (M), but not restricted to those described herein, may be imparted uniformly and consistently in cured articles. Moreover, the polyheterosiloxane composition allows for production of products with high internal homogeneity, e.g. with low haze, and high article to article consistency, as shown by the data set forth above.

[00193] The following examples are included to demonstrate various embodiments of the disclosure and are not limiting. All percentages are in weight % unless indicated otherwise. All measurements are conducted at 23°C unless indicated otherwise. Experiment I is a control for Experiment II. Experiment III is a control for Experiment IV. Experiment V is a control for Experiment VI. Example 63: (Si+Al+Eu)

[00194] 31.1g aluminum sec-butoxide stock solution (2.50 mmol/g in 2-butanol), 15.0 g 2-butanol, and 50.0 g toluene are mixed in a 250ml 3-neck flask. Under stirring 9.0 g 39% Ph₂MeSiOH heptane solution is added into the flask. The clear solution is stirred at RT for 30 minutes. 5.85g europium acetate hydrate is added to the flask and the solution is heated to 90°C for 120 minutes. A clear solution is formed. A prehydrolyzed siloxane solution is prepared by mixing 6.75g phenylmethyldimethoxysilane, 1.99g phenyltrimethoxysilane, and 1.88g 0.01M HC1 and sonicating the mixture for 20 minutes. The prehydrolyzed siloxanes solution is added to the flask. After 10 minutes, 0.34g H₂0 (10% in 2-butanol) is added to the flask. Total amount of H₂0 is -110%. Continued stirring at 90°C for 2 hours. Distilled off ~75g solvent and cool the solution to ~70°C. Solvent residue is removed using a rotary evaporator at 70°C and 10 mmHg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Euo.ioAlo.5oM^Ph2Meo.ioD^PhMeo.₂4T^Pho.o6, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

[00195] The product shows orange or red luminance with blue and near UV excitation, e.g. 320-400 nm, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm, see Figures 4. This Example does not include any of the photosensitizer.

Example 64: (Si+Al+Eu + 2-thenoyltrifluoroacetone)

[00196] 19.29g aluminum sec-butoxide stock solution (2.50 mmol/g in 2-butanol), 5.0 g 2-butanol, and 40.0 g toluene are mixed in a 100ml 3-neck flask. Under stirring 6.78g 33% Ph₂MeSiOH heptane solution is added into the flask. The clear solution is heated up to refluxing temperature and stirred for 30 minutes. 3.58g europium acetate hydrate and 3.94g 2-thenoyltrifluoroacetone (HTTA) solution (0.5wt% in toluene), as the photosensitizer, are added into flask. A clear solution is formed. A prehydrolyzed siloxane solution is prepared by mixing 3.54g phenylmethyldimethoxysilane, 1.92g phenyltrimethoxysilane, and 1.26g 0.01M HC1 and sonicating the mixture for 20 minutes. The prehydrolyzed siloxanes solution is added to the flask. After 10 minutes, 16.9g H₂0 solution (5% in 2-butanol) is added to the flask. Total amount of H₂0 is -110%. Continued stirring at refluxing temperature for 1 hour. Solvent residue is removed using a rotary evaporator at 70°C and 1 mbar. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Eu₀.ioAlo.5oM^Ph2Meo.ioD^PhMeo.2T^Pho.i(HTTA)o.ooi, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

[00197] The product shows orange or red luminance with blue and near UV excitation with a peak emission wavelength around 615 nm and a broad excitation range from 300 to 400 nm, see Figures 4.

Example 65: (Si+Zr+Tb)

[00198] 4.56g terbium acetate hydrate, 21.40g NBZ solution (80% zirconium tetrabutoxide+20% 1-butanol), and 50g toluene are charged into a 250 ml 3-neck flask and refluxed for 1 hour. A prehydrolyzed siloxane solution is prepared by mixing 7.17g phenylmethyldimethoxysilane, 3.34g phenyltrimethoxysilane, 20 g toluene, 4g butanol, and 1.25g 0.1N HC1 and sonicating the mixture for 30 minutes. The prehydrolyzed siloxanes solution is added to the flask and the solution is continued refluxing for 30 minutes. Then a mixture solution containing 0.74g H₂0 and 15g butanol is added into the flask. Total amount of H₂0 is -110%. The solution is maintained at refluxing temperature for 30 minutes. Solvent is removed using a rotary evaporator at 85°C and 1 mbar. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tbo.ioZro.4oD^PhMeo.₃sT^Pho.i5, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

[00199] The product shows green luminance with blue and near UV excitation with a peak emission wavelength around 545 nm and excitation peaks at 317, 340, 351, 369, 377, and 485 nm, see Figures 5. This Example does not include any of the photosensitizer.

Example 66: (Si+Zr+Tb + salicylic acid)

[00200] 2.18g terbium ethylhexanoate, 5.29g NBZ solution (80% zirconium tetrabutoxide+20% 1-butanol), and 20g toluene are charged into a 100 ml 3-neck flask and refluxed for 1 hour. 1.84g salicylic acid (SA) solution (lwt% in toluene), as the photosensitizer, are added into flask. A clear solution is formed. A prehydrolyzed siloxane solution is prepared by mixing 3.02g phenylmethyldimethoxysilane, 1.12g phenyltrimethoxysilane, 10 g toluene, 4g butanol, and 0.49g 0.1N HC1 and sonicating the mixture for 30 minutes. The prehydrolyzed siloxanes solution is added to the flask and the solution is continued refluxing for 30 minutes. Then a mixture solution containing 0.17g H₂0 and 3.28g butanol is added into the flask. Total amount of H₂0 is -110%. The solution is maintained at refluxing temperature for 30 minutes. Solvent is removed using a rotary evaporator at 85 °C and 1 mbar. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tbo.isZro.45D^PhMeo.₂T^Pho.i(SA)o.oo5, soluble in many organic solvents, such as butyl acetate, toluene, THF, and chloroform.

[00201] The product shows green luminance with blue and near UV excitation with a peak emission wavelength around 545 nm and a broad excitation range from 300 to 400nm, see Figures 5.

Example 67: (Si+Ti+Eu)

[00202] 3.50g europium acetate hydrate, 1.73g zinc acetate hydrate, 16.2g titanium n- butoxide, and 20g of toluene are charged into a 500 mL 3-neck flask and stirred at 60°C for 30 minutes. A pre-hydrolyzed siloxane solution is prepared by mixing 3.45g phenylmethyldimethoxysilane, 1.89g phenyltrimethoxysilane, 15g toluene and 1.85g 0.1N HC1 and sonicating the mixture for a total of 30 minutes. The solution in flask is stirred at 60°C for 4 hours after the addition of pre-hydrolyzed siloxanes solution. Total amount of H₂0 is -110%. Solvents are removed using a rotary evaporation at 80°C and 5 mmHg. The product is a white solid having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.sZno.iEuo.iD^PhMeo.₂T^Pho.i, soluble in many organic solvents such as toluene, THF, and chloroform.

[00203] The product shows red luminance with blue and near UV excitation, e.g. 320-400 nm, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 395 nm, see Figures 6. This Example does not include any of the photosensitizer.

Example 68: (Si+Ti+Eu + dibenzoylmethane)

[00204] 10.56g of europium 2-ethylhexanoate, 15.45g of titanium n-butoxide, 1.67g zinc acetate, and 50g of toluene are charged into a 250 mL 3-neck flask and stirred at 70°C until all compounds dissolved. 16.29g dibenzoylmethane (DBM) solution (lwt% in toluene), as the photosensitizer, are then added into the flask. A yellow solution is formed. A pre-hydrolyzed siloxane solution is prepared by mixing 2.48g of phenylmethyldimethoxysilane, 0.90 g of phenyltrimethoxysilane, 7g toluene and 0.83 g 0.1N HC1 and sonicated for a total of 30 minutes. The pre-hydrolyzed siloxanes solution is added to the solution in flask. 8.5g water solution (4wt in 1-butanol) is added to the flask. And the solution is stirred at 70°C for 1 hour. Total amount of H₂0 is -110%. Solvents are removed using a rotary evaporation at 85°C and 1 mbar. The product is a yellow-orange granule having mole fractions based on starting metals and siloxy units excluding counter- ions, bonded water and residual solvents of Tio_.5Zn_0.iEuo.2D^PhMeo.i5T^Pho.o5(DBM)o.oo8_> soluble in many organic solvents such as toluene, THF, and chloroform.

[00205] This product shows orange or red luminance with blue and near UV excitation with a peak emission wavelength of 615 nm and a broad excitation range from 300 to 450nm, see Figures 6.

Example 69: (Si+Ti+Eu + l,3-di(2-thienyl)-l,3-propanedione)

[00206] The Si+Ti+Eu resin are synthesized follow example 5. Then l.Og resin is dissolved in 9.0g of toluene. 2.4g l,3-di(2-thienyl)-l,3-propanedione (DTPD) solution (lwt% in toluene), as the photosensitizer, are added into resin solution. The solution changed into yellow immediately. Solvents can be removed by using a rotary evaporation at 85 °C and 1 mbar. The product is a yellow-orange granule having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.5Zno Euo.₂D^PhMeo sT^P o5(DTPD)o.oi, soluble in many organic solvents such as toluene, THF, and chloroform.

[00207] This product shows orange or red luminance with blue and near UV excitation with a peak emission wavelength of 615 nm and a broad excitation range from 300 to 470nm. The peak excitation is shifted to 440nm compared to 380nm for DBM of Example 68, see Figures 6.

Example 70: (Si+Ti+Eu + l,8-Dihvdroxy-3-methylanthraquinone)

[00208] This polyheterosiloxane composition is synthesized according to the method described relative to Example 67. Subsequently, 0.20 g of the composition is dissolved in 9.80 g of toluene. Then, 0.51 g of l,8-Dihydroxy-3-methylanthraquinone (DHMAQ) solution (lwt% in toluene), as the photosensitizer, are added to the solution causing the solution to change color to light yellow. Solvents are then removed by using a rotary evaporation at 85°C and 1 mbar. The product is a yellow- orange granule having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.5Zno.1Euo.2D ^eo.i5 o.o5(DHMAQ)o.oi, soluble in many organic solvents such as toluene, THF, and chloroform.

[00209] This product shows orange or red luminance with blue and near UV excitation with a peak emission wavelength of 615 nm and a broad excitation range from 300 to 450nm, see Figure 7.

Example 71: (Si+Ti+Eu + l-(4-biphenyl)-3-(2-nuoryl)propanedione)

[00210] 1.056g of europium 2-ethylhexanoate, 1.545g of titanium n-butoxide, 0.167g zinc acetate, and lO.Og of toluene are charged into a 50 mL flask and stirred at 70°C until all compounds dissolve. 3.54g l-(4-biphenyl)-3-(2-fluoryl)propanedione (BPFPD) solution (lwt in toluene), as the photosensitizer, are then added into the flask. A yellow solution forms. A pre-hydrolyzed siloxane solution is prepared by mixing 0.248g of phenylmethyldimethoxysilane, 0.090 g of phenyltrimethoxysilane, lg toluene and 0.083 g 0.1N HC1 and sonicated for a total of 30 minutes. The pre- hydrolyzed siloxanes solution is added to the solution in flask. 0.680g water solution (5wt in 1-butanol) is added to the flask and the solution is stirred at 70°C for 1 hour. A total amount of H20 is -110%. Solvents are removed using a rotary evaporation at 85 °C and 1 mbar. The product is a yellow-orange granule having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.5Zno.iEuo.2D^PhMeo.i5T^Pho.os(BPFPD)o.oi, soluble in many organic solvents such as toluene, THF, and chloroform.

[00211] This product shows orange or red luminance with blue and near UV excitation with a peak emission wavelength of 615 nm and a broad excitation range from 300 to 470nm.

Example 72: (Si+Ti+Eu + l-(2-naphthyl)-3-(2-fluoryl)propanedione)

[00212] This polyheterosiloxane composition is synthesized according to the method described relative to Example 67. Subsequently, 1.0 g of the polyheterosiloxane composition is dissolved in 9.0g of toluene. 3.62g l-(2-naphthyl)-3-(2- fluoryl)propanedione (NFPD) solution (lwt% in toluene), as the photosensitizer, are then added to the solution causing the solution to change color to yellow. Solvents are then removed by using a rotary evaporation at 85 °C and 1 mbar. The product is a yellow-orange granule having mole fractions based on starting metals and siloxy units excluding counter-ions, bonded water and residual solvents of Tio.5Zno.1Euo.2D ^eo.i5T o.o5(NFPD)o.oi, soluble in many organic solvents such as toluene, THF, and chloroform.

[00213] This product shows orange or red luminance with blue and near UV excitation with a peak emission wavelength of 615 nm and a broad excitation range from 300 to 470nm similar as the ligand BPFPD.

[00214] The data described above and set forth in the Figures shows that these compositions exhibit increased amplification of excitation. The aforementioned examples demonstrate that the sensitized polyheterosiloxane composition of this invention exhibits a larger peak emission intensity to at an excitation wavelength of from 320 to 440 nm as compared to control polyheterosiloxane compositions free of the photosensitizer. In addition, the sensitized polyheterosiloxane composition includes well dispersed metals because at least one oxygen atom of the siloxy units is bonded to at least one of (Ml) and/or (M2). The metals may bond with one another, further increasing the variety of the metals, and therefore the quality of the dispersion of the metals, in the sensitized polyheterosiloxane composition. The metal allows the composition to be luminescent such that excitation and emission spectra can be manipulated and customized based on choice of metal.

Synthesis of Metals^Euo^rR¹ ₂SiOwln_!rR¹SiOv7lHrR¹SiOml_L+ blue-sensitizer:

[00215] 60 ml of a 3: 1 ratio of toluene and ethanol is charged to a 1-neck 250 ml round flask equipped with reflux condenser and temperature probe. A metal alkoxide is charged to the flask followed by europium benzoate and the photo-sensitizers listed in Tables 13 below. An equimolar amount of water, with reference to europium benzoate, is added dissolved in 10 ml of a 3:1 ratio ethanol and toluene (see Table 13) at room temperature followed by heating the reaction mixture to 75 °C.

TABLE 13

Metal Europium

Examples H₂0 Photo-Sensitizer

Alkoxide Benzoate

2.455 g

0.0057 g 2,4-Dichloro-6-[l-

73 Tungsten (V) 1.031 g 0.037 g

(phenylimino) ethyl] phenol Ethoxide

4.975 g

0.0114 g 2,4-Dichloro-6-[l-

74 Tantalum (V) 2.103 g 0.074 g

(phenylimino) pthyl] phenol Ethoxide

4.975 g

0.0102 g 2-Benzoyl- 1,3-

75 Tantalum (V) 2.103 g 0.074 g

indanedione

Ethoxide Metal Europium

Examples H₂0 Photo-Sensitizer

Alkoxide Benzoate

4.975 g

0.0079 g l-(4-Biphenyl)-3-(2-

76 Tantalum (V) 2.103 g 0.074 g

fluoryl) propandione Ethoxide

5.024 g

0.0147 g 2,4-Dichloro-6-[l-

77 Niobium (V) 2.712 g 0.095 g

(phenylimino) ethyl] phenol Ethoxide

5.024 g

0.0132 g 2-Benzoyl-l,3-

78 Niobium (V) 2.712 g 0.095 g

indanedione Ethoxide

5.024 g

0.0194 g l-(4-Biphenyl)-3-(2-

79 Niobium (V) 2.712 g 0.095 g

fluoryl) propandione Ethoxide

5.651 g

0.0187 g 2,4-Dichloro-6-[l-

80 Hafnium (V) 2.061 g 0.072 g

(phenylimino) ethyl] phenol N-Butoxide

5.651 g

0.0167g 2-Benzoyl-l,3-

81 Hafnium (V) 2.061 g 0.072 g

indanedione N-Butoxide

5.651 g

0.0155 g l-(4-Biphenyl)-3-(2-

82 Hafnium (V) 2.061 g 0.072 g

fluoryl) propandione N-Butoxide

5.616 g

0.0187 g 2,4-Dichloro-6-[l-

83 Zirconium I- 2.945 g 0.103 g

(phenylimino) ethyl] phenol Propoxide

5.616 g

0.0167g 2-Benzoyl-l,3-

84 Zirconium I- 2.945 g 0.103 g

indanedione Propoxide

5.616 g

0.0222 g l-(4-Biphenyl)-3-(2-

85 Zirconium I- 2.945 g 0.103 g

fluoryl) propandione Propoxide

5.912 g

0.0224 g 2,4-Dichloro-6-[l-

86 Aluminum 4.122 g 0.144

(phenylimino) ethyl] phenol SeoButoxide

5.912 g

0.0200 g 2-Benzoyl- 1,3-

87 Aluminum 4.122 g 0.144

indanedione SeoButoxide

5.912 g

0.0311 g l-(4-Biphenyl)-3-(2-

88 Aluminum 4.122 g 0.144

fluoryl) propandione SeoButoxide

2.455 g

.0051 g 2-Benzoyl-l,3-

89 Tungsten (V) 1.031 g 0.037 g

indanedione Ethoxide

2.455 g

.0079 g l-(4-Biphenyl)-3-(2-

90 Tungsten (V) 1.031 g 0.037 g

fluoryl) propandione Ethoxide [00216] The 2-Benzoyl-l,3-indanedione is purchased commercially from Alfa Aesar and used unpurified.

[00217] The ,4-dichloro-6-[l-(phenylimino)ethyl]phenol is synthesized according to the experimental procedure given by T.B. Nguyen, Q. Wang, F. Gueritte, Synthetic Comm., 2012, 42, 2648.

[00218] The -(4-biphenyl)-3-(2-fluoryl)propandione is synthesized according to the experimental procedure given by V. Divya, R.O. Freire, M.L.P. Reddy, Dalton Trans., 2011, 40, 3257.

[00219] The reaction mixtures are stirred for 2 hours at 75 °C then the pre- hydrolyzed siloxane moieties are added. After 15 min the residual amount of water is added dissolved in 10 ml ratio ethanol and toluene at 3:1 ratio.

[00220] The pre -hydrolyzed siloxane moieties are formed by mixing varying amounts of the compounds below in 0.01M HC1 and sonicating the mixtures for 20 minutes.

TABLE 14

[00221] The reaction mixtures is stirred for further 2 hours at 75 °C, cooled to ambient and then filtered through 0.45 μιη PTFE filter media. Solvents and other volatiles are removed using rotary evaporation at 75°C and 15 mmHg resulting in solid products. The products show orange or red luminance with blue excitation, with a peak emission wavelength around 615 nm and a peak excitation wavelength around 450 nm.

[00222] This data shows that various transition metals and europium metal containing polyheterosiloxane compositions incorporated with a blue-photosensitizer were successfully synthesized and display red emission around 615 nm with amplified excitation at approximately 450 nm.

Cured Films

[00223] 0.75 g of Ml^o.eEuo.iIR^SiOMlm^SiOa/zldtR^iOi/zlt + blue- sensitizer is dissolved in 2.5 ml toluene and added to 9.5 g of part B of DOW CORNING^® OE-6570 A/B KIT and the solvent removed in vacuum. 4.75 g of part A is added to the mixture and thoroughly mixed in a planetary mixer. Cured films are prepared using a mold under a hot press at 5000 psi for lh at 120°C. The cured films are 3 mm thick and include approximately 5 wt.% of Ml/2o.6Euo.2[R¹2Si0₂/2]m[ ¹Si032]d[ ¹SiOi/2]d + blue-sensitizer (see Table 15).

TABLE 15

[00224] This data shows that various metal containing polyheterosiloxane compositions can be incorporated into curable silicone compositions to produce either a free standing article or an article that includes a substrate and a coating disposed on the substrate, wherein the coating includes the cured product of the silicone composition.

Further Examples:

[00225] A polyheterosiloxane composition having the formula Metalo.6Euo.2[PhMeSi0₂/2]o.i5[PhSiC>3 2]o.o5 where 'Metal' is chosen from Ti, W, Al, Zr and Hf is formed as described above. More specifically, 60 ml of a 3 : 1 ratio of toluene and ethanol is charged to a 1-neck 250 ml round flask equipped with reflux condenser and temperature probe. A metal alkoxide is charged to the flask followed by europium benzoate and the photo- sensitizers. An equimolar amount of water, with reference to europium benzoate, is added dissolved in 10 ml of a 3: 1 ratio ethanol and toluene at room temperature followed by heating the reaction mixture to 75 °C. Subsequently, a 1 wt solution dissolved in toluene was prepared. A sensitizer ligand was added to a 2.5 ml sample of this solution, resulting in a 1:100 ligand: europium molar ratio. The identity of the Metal and photosensitizer are shown in Table 16 below. All samples were measured via an Fluorolog 3 spectrofluorometer, resulting in red luminescence with a dominant emission peak about 615 nm with a Full Width Half Maximum (FWHM) of less than 12 nm.

TABLE 16

Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

]bis(4-Nitro phenol)

115 75 Hf 61707-51-5 3-Benzoyl-2-phenyl-lH-quinolin-4-one l-(2,3-Dihydro-lH-benzocyclopentaqui

116 75 Ti 331674-51-2

nolin-4-yl) -2-naphthol

117 75 Ti 71752-57-3 2-( 1 -Phenylbenzoquinolin-3 -yl)-phenol

1,1'-[1,2-

118 25 W 155062-61-6 Cyclohexanediylbis(nitrilomethylidyne)

]bis-2-naphthalenol

2,2'-[l,2-

119 25 W 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol) l-(2,3-Dihydro-lH-benzocyclopentaqui

120 25 W 331674-51-2

nolin-4-yl) -2-naphthol

1,1'-[1,2-

121 25 Ti 155062-61-6 Cyclohexanediylbis(nitrilomethylidyne)

]bis-2-naphthalenol

122 25 Ti 71752-57-3 2-( 1 -Phenylbenzoquinolin-3 -yl)-phenol

2,2'-[l,2-

123 25 Ti 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol)

2,2'- [ 1 ,2-Phenylenebis(nitrilomethylidy

124 25 Ti 85573-11-1

ne)]bis[4-chlorophenol]

125 25 Hf 65182-56-1 2-(l ,8-Naphthyridin-2-yl)phenol

126 25 Hf 61707-51-5 3-Benzoyl-2-phenyl-lH-quinolin-4-one

6-Fluoro-3-[(4- methoxyphenyl)c arbonyl] quinolin-

1326908-84-

127 75 Ti 4(lH)-one 6-fluoro-3-[(4- 2

methoxyphenyl)c arbonyl] quinolin- 4(lH)-one

1325306-91-

128 75 Ti 3-Benzoyl-6-fluoro-4(lH)-quinolinone

9

7-(l,3-Benzodioxol-5- ylcarbonyl) [1,3] dioxolo [4,5-

1326806-77- G]quinolin-8(5H)-one 7-(l,3-

129 75 Ti

2 benzodioxol-5- ylcarbonyl) [1,3] dioxolo [4,5-

G]quinolin-8(5H)-one

3 - ( 1 , 3 -Benzodioxol- 5 -ylc arbonyl) -

130 75 Ti 769972-66-9

4( 1 H)-quinolinone

2-(4-Methoxybenzoyl)-lH-indene-

131 75 Ti 147847-17-4

l,3(2H)-dione

3-Benzoyl-6,8-difluoro-4(lH)-

132 75 Ti 892285-96-0

quinolinone Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

133 75 Ti 708-06-5 2-Hydroxy- 1 -naphthaldehyde

134 75 Ti 574-19-6 2'-Hydroxy- 1 '-acetonaphthone

135 75 Ti 85-19-8 5-Chloro-2-hydroxybenzophenone

136 75 Ti 3321-92-4 3 ',5 '-Dichloro-2'-hydroxyacetophenone

137 75 Ti 117-99-7 2-Hydroxybenzophenone

138 75 Ti 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

139 75 Ti 117-99-9 2',5-Dichloro-2-hydroxybenzophenone

140 75 Ti 1450-74-4 5'-Chloro-2'-hydroxyacetophenone

2',5-Dichloro-2-hydroxy-4-

141 75 Ti 263554-77-4

methylbenzophenone

2-(4-Methoxybenzoyl)-lH-indene-

142 75 W 147847-17-4

l,3(2H)-dione

143 75 W 708-06-5 2-Hydroxy- 1 -naphthaldehyde

2-(4-Methoxybenzoyl)-lH-indene-

144 75 Hf 147847-17-4

l,3(2H)-dione

6-Fluoro-3-[(4- methoxyphenyl)c arbonyl] quinolin-

1326908-84-

145 75 Hf 4(lH)-one 6-fluoro-3-[(4- 2

methoxyphenyl)c arbonyl] quinolin- 4(lH)-one

1325306-91-

146 75 Hf 3-Benzoyl-6-fluoro-4(lH)-quinolinone

9

7-(l,3-Benzodioxol-5- ylcarbonyl) [1,3] dioxolo [4,5-

1326806-77- G]quinolin-8(5H)-one 7-(l,3-

147 75 Hf

2 benzodioxol-5- ylcarbonyl) [1,3] dioxolo [4,5-

G]quinolin-8(5H)-one

148 75 Hf 708-06-5 2-Hydroxy- 1 -naphthaldehyde

149 75 Hf 85-19-8 5-Chloro-2-hydroxybenzophenone

150 75 Hf 3321-92-4 3 ',5 '-Dichloro-2'-hydroxyacetophenone

151 75 Hf 117-99-7 2-Hydroxybenzophenone

152 75 Hf 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

153 75 Hf 117-99-9 2',5-Dichloro-2-hydroxybenzophenone

154 75 Hf 1450-74-4 5'-Chloro-2'-hydroxyacetophenone

2',5-Dichloro-2-hydroxy-4-

155 75 Hf 263554-77-4

methylbenzophenone

156 75 W 574-19-6 2'-Hydroxy- 1 '-acetonaphthone

157 75 W 85-19-8 5-Chloro-2-hydroxybenzophenone

6-Fluoro-3-[(4-

1326908-84-

158 75 Zr methoxyphenyl)c arbonyl] quinolin- 2

4(lH)-one 6-fluoro-3-[(4- Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

methoxyphenyl)c arbonyl] quinolin- 4(lH)-one

2-(4-Methoxybenzoyl)-lH-indene-

159 75 Zr 147847-17-4

l,3(2H)-dione

160 75 Zr 708-06-5 2-Hydroxy- 1 -naphthaldehyde

161 75 Zr 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

162 75 Zr 1450-74-4 5'-Chloro-2'-hydroxyacetophenone

6-Fluoro-3-[(4- methoxyphenyl)c arbonyl] quinolin-

1326908-84-

163 25 Hf 4(lH)-one 6-fluoro-3-[(4- 2

methoxyphenyl)c arbonyl] quinolin- 4(lH)-one

2-(4-Methoxybenzoyl)-lH-indene-

164 25 Hf 147847-17-4

l,3(2H)-dione

165 25 Hf 708-06-5 2-Hydroxy- 1 -naphthaldehyde

166 25 Hf 85-19-8 5-Chloro-2-hydroxybenzophenone

167 25 Hf 3321-92-4 3 ',5 '-Dichloro-2'-hydroxyacetophenone

168 25 Hf 117-99-7 2-Hydroxybenzophenone

169 25 Hf 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

170 25 Hf 117-99-9 2',5-Dichloro-2-hydroxybenzophenone

171 25 Hf 1450-74-4 5'-Chloro-2'-hydroxyacetophenone

2',5-Dichloro-2-hydroxy-4-

172 25 Hf 263554-77-4

methylbenzophenone

6-Fluoro-3-[(4- methoxyphenyl)c arbonyl] quinolin-

1326908-84-

173 25 Ti 4(lH)-one 6-fluoro-3-[(4- 2

methoxyphenyl)c arbonyl] quinolin- 4(lH)-one

1325306-91-

174 25 Ti 3-Benzoyl-6-fluoro-4(lH)-quinolinone

9

7-(l,3-Benzodioxol-5- ylcarbonyl) [1,3] dioxolo [4,5-

1326806-77- G]quinolin-8(5H)-one 7-(l,3-

175 25 Ti

2 benzodioxol-5- ylcarbonyl) [1,3] dioxolo [4,5-

G]quinolin-8(5H)-one

2-(4-Methoxybenzoyl)-lH-indene-

176 25 Ti 147847-17-4

l,3(2H)-dione

3-Benzoyl-6,8-difluoro-4(lH)-

177 25 Ti 892285-96-0

quinolinone

178 25 Ti 708-06-5 2-Hydroxy- 1 -naphthaldehyde

179 25 Ti 574-19-6 2'-Hydroxy- 1 '-acetonaphthone

180 25 Ti 85-19-8 5-Chloro-2-hydroxybenzophenone Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

181 25 Ti 3321-92-4 3 ',5 '-Dichloro-2'-hydroxyacetophenone

182 25 Ti 117-99-7 2-Hydroxybenzophenone

183 25 Ti 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

184 25 Ti 117-99-9 2',5-Dichloro-2-hydroxybenzophenone

185 25 Ti 1450-74-4 5'-Chloro-2'-hydroxyacetophenone

2',5-Dichloro-2-hydroxy-4-

186 25 Ti 263554-77-4

methylbenzophenone

2-(4-Methoxybenzoyl)-lH-indene-

187 25 W 147847-17-4

l,3(2H)-dione

188 25 W 708-06-5 2-Hydroxy- 1 -naphthaldehyde

189 25 W 574-19-6 2'-Hydroxy- 1 '-acetonaphthone

190 25 W 85-19-8 5-Chloro-2-hydroxybenzophenone

191 25 W 117-99-7 2-Hydroxybenzophenone

192 25 W 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

6-Fluoro-3-[(4- methoxyphenyl)c arbonyl] quinolin-

1326908-84-

193 25 Zr 4(lH)-one 6-fluoio-3-[(4- 2

methoxyphenyl)c arbonyl] quinolin- 4(lH)-one

3 - ( 1 , 3 -Benzodioxol- 5 -ylc arbonyl) -

194 25 Zr 769972-66-9

4( 1 H)-quinolinone

2-(4-Methoxybenzoyl)-lH-indene-

195 25 Zr 147847-17-4

l,3(2H)-dione

3-Benzoyl-6,8-difluoro-4(lH)-

196 25 Zr 892285-96-0

quinolinone

197 25 Zr 2549-87-3 4-Allyloxy-2-hydroxybenzophenone

198 25 Zr 1450-74-4 5'-Chloro-2'-hydroxyacetophenone

199 75 Ti 2980-33-8 2-Hydroxy- 3 , 5 -dinitropyridine

200 75 Ti 7464-14-4 2-Hydroxy- 5 -methyl- 3 -nitropyridine

1,1'-[1,2-

201 75 Ti 155062-61-6 Cyclohexanediylbis(nitrilomethylidyne)

]bis-2-naphthalenol

2,2'- { Ethane- 1 ,2-diylbis [nitrilo( le)eth- 1 -yl- 1 -ylidene] } diphenol 2- [( 1 e)-N-

202 75 Ti 5464-60-8 ((E)-2-{ [(E)-l-(2- hydroxyphenyl)ethylidene] amino } ethyl )ethanimidoyl]phenol

2,3-dihydro-3-[(4-

203 75 Ti 136860-64-5

methylphenyl)imino] - 1 H-inden-4-ol

2,2'-[l,2-

204 75 W 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol)

205 75 W 2980-33-8 2-Hydroxy- 3 , 5 -dinitropyridine Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

206 75 W 5464-60-8 ((E)-2-{ [(E)-l-(2- hydroxyphenyl)ethylidene] amino } ethyl )ethanimidoyl]phenol

207 75 Zr 6332-56-5 2-Hydroxy-3-nitropyridine

2,2'-[l,2-

208 75 Ti 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol)

2,2'-[l,2-

209 75 Hf 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol)

210 75 Hf 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

211 75 Hf 6332-56-5 2-Hydroxy-3-nitropyridine

212 75 Hf 7464-14-4 2-Hy droxy- 5 -methyl- 3 -nitropyridine

213 75 Hf 2980-33-8 2-Hy droxy- 3 , 5 -dinitropyridine

214 75 Hf 39745-39-6 2-Hydroxy-6-methyl-3-nitropyridine

2,3-dihydro-3-[(4-

215 75 Hf 136860-64-5

methylphenyl)imino] - 1 H-inden-4-ol

216 75 Ti 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

2,2'- [ 1 ,2-Phenylenebis(nitrilomethylidy

217 75 Ti 85573-11-1

ne)]bis[4-chlorophenol]

218 75 Ti 39745-39-6 2-Hydroxy-6-methyl-3-nitropyridine

219 75 W 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone l-[(2-Chloro-4-nitrophenyl)diazenyl]-

220 75 W 2814-77-9

2-naphthol

221 75 Zr 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

222 75 Zr 7464-14-4 2-Hy droxy- 5 -methyl- 3 -nitropyridine

223 75 Zr 2980-33-8 2-hy droxy- 3 , 5 -dinitropyridine

2,3-dihydro-3-[(4-

224 75 Zr 136860-64-5

methylphenyl)imino] - 1 H-inden-4-ol

225 25 Hf 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

226 25 Ti 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

227 25 W 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

228 25 Zr 1481-27-2 4'-Fluoro-2'-hydroxyacetophenone

229 25 Ti 5464-60-8 ((E)-2-{ [(E)-l-(2- hydroxyphenyl)ethylidene] amino } ethyl )ethanimidoyl]phenol

2,2'- [ 1 ,2-Phenylenebis(nitrilomethylidy

230 25 Ti 85573-11-1

ne)]bis[4-chlorophenol] Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

1,1'-[1,2-

231 25 Ti 155062-61-6 Cyclohexanediylbis(nitrilomethylidyne)

]bis-2-naphthalenol

2,2'-[l,2-

232 25 Hf 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol)

2,2'-[l,2-

233 25 Ti 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol)

2,2'-[l,2-

234 25 W 335104-79-5 Cyclohexanediylbis(nitrilomethylidyne)

]bis(4-Nitro phenol) l-[(2-Chloro-4-nitrophenyl)diazenyl]-

235 25 W 2814-77-9

2-naphthol

236 25 Ti 1450-76-6 2'-Hydroxy-5'-nitroacetophenone

237 25 Hf 6332-56-5 2-Hydroxy-3-nitropyridine

238 25 Ti 6332-56-5 2-Hydroxy-3-nitropyridine

239 25 Zr 6332-56-5 2-Hydroxy-3-nitropyridine

240 25 Hf 7464-14-4 2-Hy droxy- 5 -methyl- 3 -nitropyridine

241 25 Ti 7464-14-4 2-Hy droxy- 5 -methyl- 3 -nitropyridine

242 25 W 7464-14-4 2-Hy droxy- 5 -methyl- 3 -nitropyridine

243 25 Zr 7464-14-4 2-Hy droxy- 5 -methyl- 3 -nitropyridine

244 25 Hf 2980-33-8 2-Hy droxy- 3 , 5 -dinitropyridine

245 25 Ti 2980-33-8 2-Hy droxy- 3 , 5 -dinitropyridine

246 25 Zr 2980-33-8 2-Hy droxy- 3 , 5 -dinitropyridine

247 25 Hf 39745-39-6 2-Hydroxy-6-methyl-3-nitropyridine

248 25 Ti 39745-39-6 2-Hydroxy-6-methyl-3-nitropyridine

249 25 Zr 39745-39-6 2-Hydroxy-6-methyl-3-nitropyridine

250 25 Ti 5464-60-8 ((E)-2-{ [(E)-l-(2- hydroxyphenyl)ethylidene] amino } ethyl )ethanimidoyl]phenol

2,3-dihydro-3-[(4-

251 25 Hf 136860-64-5

methylphenyl)imino] - 1 H-inden-4-ol

2,3-dihydro-3-[(4-

252 25 Ti 136860-64-5

methylphenyl)imino] - 1 H-inden-4-ol

4-Chloro-2-[l-(l-

253 75 Ti 105558-35-8

naphthalenylimino)ethyl]-phenol

2,2'- [ 1 ,2-Phenylenebis(nitrilomethylidy

254 75 Ti 85573-11-1

ne)]bis[4-chlorophenol]

2-(7-Phenyl-[l,2,4]triazolo[l,5-

255 75 W 180141-32-6

A]pyrimidin-5 -yl)phenol Rxn

Primary CAS

Ex. Temp Name

Metal Number

(°C)

l-(2,3-Dihydro-lH-benzocyclopentaqui

256 75 W 331674-51-2

nolin-4-yl)-2-naphthol

[00226] One or more of the values described above may vary by ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. The disclosure is illustrative including words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced otherwise than as specifically described herein. In additional non- limiting embodiments, all values and ranges of values within any aforementioned range of numbers are hereby expressly contemplated.

[00227] One or more of the values described above may vary by ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. The disclosure is illustrative including words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced otherwise than as specifically described herein.

[00228] In various non-limiting embodiments, this disclosure expressly contemplates and herein affirmatively includes one or more components, articles, method steps, analytical determinations, compounds, and/or physical properties described in one or more of U.S. Provisional Patent Application Serial Numbers 61/662,199; 61/662,201; 61/662,171; 61/662,192; 61/662,180; 61/662,249; 61/662,264; 61/662,276; 61/782,628; 61/782,230; 61/784,581; 61/783,036; 61/784,311; 61/851,990; 61/783,797; 61/781,808; 61/781,818; 61/781,827; 61/785,834; 61/786,102; 61/784,741; 61/785,352; 61/784,823; and/or 61/785,134, each of which is expressly incorporated herein by reference in its entirety in one or more non-limiting embodiments. Moreover, this application expressly claims priority to each of the immediately aforementioned U.S. Provisional Patent Applications independently.

Claims

CLAIMS What is claimed is:

1. A polyheterosiloxane composition comprising:

(A) a first metal (Ml),

(B) a second metal (M2),

(C) siloxy units having the formula (R^SiOm), (R^SiO^), (R¹Si0_{3 2}), and/or (Si0_4/2),

wherein each R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms,

wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹ ₃Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si03/2]t[Si04/2]_q, wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9,

wherein m, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q

~ 1,

wherein at least one oxygen atom of said siloxy units is bonded to at least one of (Ml) and/or (M2),

wherein at least one of (Ml) and (M2) is a lanthanide metal, and wherein said composition exhibits a quantum yield of at least 0.05%.

2. The polyheterosiloxane composition of claim 1 wherein one of (Ml) and (M2) is a non-lanthanide metal and the other of (Ml) and (M2) is a lanthanide metal.

3. The polyheterosiloxane composition of claim 1 or 2 wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹ ₂Si0_2/2]_d[R¹Si0₃/₂]t wherein a is from 0.1 to 0.8, b is from 0.05 to 0.5, and each of d and t is independently from 0.1 to 0.8.

4. The polyheterosiloxane composition of any preceding claim having a quantum yield of at least 5%.

5. The polyheterosiloxane composition of any preceding claim wherein (Ml) is chosen from Ti, Zr, Al, Zn, Hf, Ta, Y, Nb and combinations thereof and (M2) is chosen from Ce, Eu, Nd, Er, Sm, Dy, Tb, and combinations thereof.

6. The polyheterosiloxane composition of any preceding claim having a total life time measurement of from 0.4 to 1.6 milliseconds and an asymmetry ratio of from 3.0 to 6.0.

7. The polyheterosiloxane composition of any preceding claim comprising -(Si-0-Ml-0-M2)- bonds.

8. The polyheterosiloxane composition of any preceding claim wherein one of (Ml) and (M2) is Eu³⁺.

9. The polyheterosiloxane composition of any preceding claim that emits light having a peak of from 610 to 620 nm.

10. The polyheterosiloxane composition of any one of claims 1-8 that:

(i) emits light having a wavelength of 400 to 1700 nm when excited by a light source having a wavelength of 200 to 1000 nm; or

(ii) emits light having a wavelength of 450 to 750 nm when excited by a light source having a wavelength of 250 to 520 nm; or

(iii) emits visible light having a wavelength of 450 to 650 nm when excited by UV light; or

(iv) emits infrared light having a wavelength of 1450 to 1650 nm when excited by light having a wavelength from 650 to 5,000 nm; or

(v) emits near IR light having a wavelength of 1000 to 1100 nm when excited by light having a wavelength from 650 to 5,000 nm,

with the proviso that the emitted light has a longer wavelength than the excitation light source.

11. The polyheterosiloxane composition of any preceding claim wherein at least one of the R¹ groups is phenyl.

12. The polyheterosiloxane composition of any one of claims 1- 10 wherein the siloxy units have the formula [(CH3)(C6H5)Si0₂/₂M(C6H5)SiC>3/₂]t and/or [(C₆H₅)2Si0_2/2]_d [(C₆H₅)Si03/₂ ]t.

13. The polyheterosiloxane composition of any one of claims 1- 12 further comprising a photosensitizer present in an amount of less than 3 moles of photosensitizer per one mole of the lanthanide metal,

wherein said photosensitizer imparts a larger peak emission intensity to said sensitized polyheterosiloxane composition at an excitation wavelength of from 320 to 480 nm as compared to a control polyheterosiloxane composition free of the photosensitizer.

14. The polyheterosiloxane composition of claim 13 wherein said photosensitizer is present in an amount of from 0.0001 to 0.04 moles of photosensitizer per one mole of the lanthanide metal.

15. The polyheterosiloxane composition of claim 13 or 14 wherein said photosensitizer is chosen from (i) a β-diketone, (ii) a β-diketonate, (iii) a salicylic acid, (iv) an aromatic carboxylic acid, (v) an aromatic carboxylate, (vi) a polyaminocarboxylic acid, (vii) a polyaminocarboxylate, (viii) a N-heterocyclic aromatic compound, (ix) a Schiff base, (x) a phenol, (xi) an aryloxide, and combinations thereof.

16. The polyheterosiloxane composition of claim 13 or 14 wherein said photosensitizer is a β-diketone or a β-diketonate.

17. The polyheterosiloxane composition of claim 13 or 14 wherein said photosensitizer is an aromatic carboxylic acid or aromatic carboxylate.

18. The polyheterosiloxane composition of claim 13 or 14 wherein said photosensitizer is a salicylic acid or a salicylate.

19. The polyheterosiloxane composition of any preceding claim wherein (Ml) or (M2) is Al, Zr, or combinations thereof.

20. The polyheterosiloxane composition of any preceding claim that is soluble in a hydrocarbon solvent.

21. A silicone composition comprising the polyheterosiloxane composition of any preceding claim and a silicone fluid.

22. A method for preparing the polyheterosiloxane composition of any one of claims 1-12 comprising the step of reacting:

(A') a metal (M3) alkoxide,

(B ') an optional hydrolyzable metal (M4) salt,

(C) a silicon-containing material having silicon-bonded hydroxy groups, and

(D) an amount of water that provides between 50 and 200% necessary to hydrolyze and condense hydrolyzable groups of (AO and optionally (Β'),

wherein at least one of (M3) and (M4) is a lanthanide metal.

23. The method of claim 22 wherein the (C) silicon-containing material having silicon-bonded hydroxy groups is chosen from (C 1) siloxane having silicon- bonded hydroxy groups, (C'2) a silane having silicon-bonded hydroxy groups, and combinations thereof.

24. The method of claim 22 or 23 wherein (C) comprises R⁵ _g(R⁶0)f(HO)jSiO(4-(f₊g₊j))/2 and/or R⁵ _h(HO)_kSiZ'i, wherein R⁵ is hydrogen or a hydrocarbyl group, and at least one R⁶ is hydrogen.

25. The method of any one of claims 22-24 wherein (Α') is chosen from titanium tetraisopropoxide, titanium butoxide, zirconium tetrabutoxide, and aluminum sec-butoxide.

26. The method of any one of claims 22-25 wherein (Ε ) is chosen from

(Ε 1) a non-hydrated metal salt having a general formula (IV) R^_eM4(Z)(_v2__e)/_w and

(Ε 2) a hydrated metal salt having a general formula (V) M4(Z)_v2/_w-xH20, (M4) is a lanthanide metal, v2 is the oxidation state of M4, w is the oxidation state of Z, Z is independently chosen from alkoxides, carboxylates, β-diketonates, chlorides, organic sulfonates, nitrates, and oxalates, each R^ is an independently selected alkyl group having 1 to 18 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, or aryl group having from 6 to 18 carbon atoms, e is a value from 0 to 3 and x is a value from 0 to 12.

27. A polyheterosiloxane composition formed from the method of any one of claims 22 to 26.

28. The method of any one of claims 22-26 further comprising the step of (II) introducing a photosensitizer to one or more of (Α'), (Β'), (C), and (D) prior to the step of reacting and/or introducing the photosensitizer to the polyheterosiloxane composition,

wherein the photosensitizer is present in the polyheterosiloxane composition in an amount of less than 3 moles of photosensitizer per one mole of the lanthanide metal, and

wherein the photosensitizer imparts a larger peak emission intensity to the sensitized polyheterosiloxane composition at an excitation wavelength of from 320 to 480 nm as compared to a control polyheterosiloxane composition free of the photosensitizer.

29. The method of any one of claims 22-28 wherein (Ml) or (M2) is Al, Zr, or combinations thereof.

30. A polyheterosiloxane composition formed from the method of any one of claims 22 to 28.

31. A silicone composition comprising:

(I) a polyheterosiloxane composition comprising;

(A) a first metal (Ml),

(B) a second metal (M2),

(C) siloxy units having the formula

(R¹Si0_{3 2}),

wherein R¹ is independently a hydrocarbon or halogenated hydrocarbon group comprising 1 to 30 carbon atoms,

wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹ ₃Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si03/2]t[Si04/2]_q, wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9, and

wherein m, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1, and

(II) a curable silicone.

32. The silicone composition of claim 31 wherein at least one of (Ml) and (M2) is a lanthanide metal.

33. The silicone composition of claim 31 or 32 wherein said polyheterosiloxane composition exhibits a quantum yield of at least 0.05%.

34. The silicone composition of any one of claims 31-33 wherein at least one oxygen atom of said siloxy units is bonded to at least one of (Ml) and/or (M2).

35. The silicone composition of any one of claims 31-34 wherein one of (Ml) and (M2) is a non-lanthanide metal and the other of (Ml) and (M2) is a lanthanide metal.

36. The silicone composition of any one of claims 31-35 wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula [(Ml)]_a[(M2)]_b[R¹ ₂Si0_2/2]_d[R¹Si0₃/₂]t wherein a is from 0.1 to 0.8, b is from 0.05 to 0.5, and each of d and t is independently from 0.1 to 0.8.

37. The silicone composition of any one of claims 31-36 wherein (Ml) is chosen from Ti, Zr, Al, Zn, Hf, Ta, Y, Nb and combinations thereof and (M2) is chosen from Ce, Eu, Nd, Er, Sm, Dy, Tb, and combinations thereof.

38. The silicone composition of any one of claims 31-37 wherein said polyheterosiloxane composition has a total life time measurement of from 0.4 to 1.6 milliseconds and an asymmetry ratio of from 3.0 to 6.0.

39. The silicone composition of any one of claims 31-38 wherein said polyheterosiloxane composition comprises -(Si-0-Ml-0-M2)- bonds.

40. The silicone composition of any one of claims 31-39 wherein one of (Ml) and (M2) is Eu³⁺.

41. The silicone composition of any one of claims 31-40 that emits light having a peak of from 610 to 620 nm.

42. The silicone composition of any one of claims 31-40 that:

43. The silicone composition of any one of claims 31-42 wherein at least one of said R¹ groups is phenyl.

44. The silicone composition of any one of claims 31-42 wherein said siloxy units have the formula [(CH3)(C6H5)Si0₂/₂M(C6H5)SiC>3/₂]t and/or [(C₆H₅)2Si0_2/2]_d [(C₆H₅)Si03/₂ ]t.

45. The silicone composition of any one of claims 31-44 wherein said polyheterosiloxane composition is soluble in a hydrocarbon solvent.

46. A silicone composition of any one of claims 31-45 further comprising a silicone fluid different from said (II) curable silicone.

47. The silicone composition of any one of claims 31-46 wherein said curable silicone is hydrosilylation-curable.

48. The silicone composition of any one of claims 31-46 wherein said curable silicone is condensation-curable.

49. The silicone composition of claim 48 wherein said curable silicone comprises a cross-linking agent having at least one silicon-bonded hydrolysable group.

50. The silicone composition of claim 49 wherein said cross-linking agent has the formula R^qSiXzi.q, wherein is a C\ to Cg hydrocarbyl group or a C\ to Cg halogen-substituted hydrocarbyl group, X is a hydrolysable group, and q is 0 or 1.

51. The silicone composition of claim 31 wherein one of (Ml) and (M2) is Al, Zr, or combinations thereof.

52. A cured product of said silicone composition of any one of claims 31-

51.

53. An article comprising:

a substrate; and

a coating disposed on said substrate, wherein said coating comprises the cured product of a silicone composition comprising;

(I) a polyheterosiloxane composition comprising;

(A) a first metal (Ml),

(B) a second metal (M2),

(C) siloxy units having the formula (R^SiOm), (R^SiO^), (R¹Si0_{3 2}), and/or (Si0_{4 2})

wherein the mole fractions of (A), (B), and (C) relative to each other is of the formula

[(Ml)]_a[(M2)]_b[R¹ ₃Si0_1/2]_m[R¹ ₂Si0_2/2]_d[R¹Si0₃/2]t[Si0_4/2]_q,

wherein a is from 0.001 to 0.9, b is from 0.001 to 0.9, m is from zero to 0.9, d is from zero to 0.9, t is from zero to 0.9, and q is from zero to 0.9, and

wherein m, d, t, and q cannot all be zero and the sum of a+b+m+d+t+q ~ 1 , and

(II) a curable silicone.

54. The article of claim 53 wherein said coating has an average thickness of from 1 to 100 μιη.

55. The article of claim 53 or 54 wherein said substrate is further defined as a release liner.