CN113278035B - 一类电刺激响应型铱（ⅲ）配合物及其应用 - Google Patents
一类电刺激响应型铱（ⅲ）配合物及其应用 Download PDFInfo
- Publication number
- CN113278035B CN113278035B CN202110566098.7A CN202110566098A CN113278035B CN 113278035 B CN113278035 B CN 113278035B CN 202110566098 A CN202110566098 A CN 202110566098A CN 113278035 B CN113278035 B CN 113278035B
- Authority
- CN
- China
- Prior art keywords
- complex
- iii
- ligand
- electron
- iridium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000004044 response Effects 0.000 title claims abstract description 16
- 230000000638 stimulation Effects 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 230000008859 change Effects 0.000 claims abstract description 13
- 230000002441 reversible effect Effects 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 230000002468 redox effect Effects 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000003993 interaction Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical group CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003368 amide group Chemical group 0.000 abstract description 4
- QTQLUUDYDWDXNA-UHFFFAOYSA-N 1-ethyl-4-(1-ethylpyridin-1-ium-4-yl)pyridin-1-ium Chemical compound C1=C[N+](CC)=CC=C1C1=CC=[N+](CC)C=C1 QTQLUUDYDWDXNA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 31
- 229910052723 transition metal Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 description 15
- 239000012279 sodium borohydride Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 150000003624 transition metals Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 8
- -1 transition metal iridium (III) complexes Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 1
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 description 1
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1503—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
本发明公开了一类电刺激响应型铱(Ⅲ)配合物及其应用，通过在配合物的C^N配体的苯环或吡啶环的不同位点上修饰乙基吡啶盐单元构建紫精配体，而N^N配体上引入吸电子的酰胺基团或给电子的甲基后构成；其主要利用紫精结构可逆的氧化还原特性，结合给电子或吸电子基团对配合物电子转移态的影响，在外界刺激下，改变铱(Ⅲ)配合物的电子转移态而改变配合物的光物理性质，可实现肉眼可见的光颜色的多彩变化，可应用于信息存储和加密领域；在紫精类结构单元的氮原子上引入乙基基团后，使得带有乙基紫精配体的铱(Ⅲ)配合物具有良好的氧化还原可逆性和化学稳定性，在电致变色器件、信息存储器件、储能器件中可以有着良好的应用前景。
Description
技术领域：
本发明属于有机光电材料技术领域，具体涉及一类基于紫精配体的电刺激响应型铱 (Ⅲ)配合物及其应用。
背景技术：
近年来，具有光、电等刺激性响应的发光材料在生物医学与成像、光电器件、传感器、信息防伪与加密保护等领域有着重要的应用。目前，光、电刺激响应性材料主要包括螺吡喃类、偶氮苯类、二芳基乙烯类和紫精类化合物。其中，紫精类化合物材料具备优良的氧化还原可逆性，独特的光物理、光化学性质和电化学性质，是一类应用广泛的光电转换、光致变色和电致变色材料。
紫精类化合物主要的工作机理是：接收外界刺激，如电场或者光刺激后，在富电子无机阴离子或有机配体的协助下，发生电子转移，完成两步还原反应，表现出三种不同的状态(中性的V0、单自由基V·+和双电荷V2+)，这三种状态具有不同电子分布形式，导致不同的电子吸收带，继而伴随着材料颜色的改变。在信息存储器件中，紫精类化合物由于其阳离子形式与自由基形式之间的转换，使可见光区域发生吸收变化，实现信息变化与记录。此外，紫精类化合物上的氮原子的取代基不同，会影响其还原电位，从而影响其光物理性质。现今对紫精类化合物的研究一般集中在纯有机小分子上，主要致力于改变材料颜色，以发光作为信号输出的研究较少。而光是可以以极高的灵敏度检测到的信号之一，如能实现光信号输出将拓宽该类材料的应用前景，但是，值得注意的一点是，将外界刺激处理成发光信号的分子还需考虑它们的发光量子效率。
过渡金属铱(Ⅲ)配合物具有发光量子产率高、发光寿命长、斯托克斯位移大、光稳定性高、发光颜色易于调控和具有很强的自旋-轨道耦合等优异的光物理性质，在有机光电领域得到了广泛的研究和应用。并且，磷光铱(Ⅲ)配合物分子具有丰富的激发态性质，包括配体和金属间能量传递(MLCT)态、配体内部的能量传递(ILCT)态、配体与配体之间的能量传递(LLCT)态等，可以通过对配体的修饰而引起一系列激发态的变化。将紫精单元引入到铱(Ⅲ)配合物中，可以在传统的基础上，结合紫精结构的可逆氧化还原性质，应用于光电转换、电致变色器件中。如中国专利CN 105237578 B 公开的具有多重刺激响应特性的磷光铱配合物及其应用，其利用离子型过渡金属配合物电子捕获能力强，良好的刺响应性，通过改变主配体结构以及辅助配体上烷基链的结构，可实现发光性质的可逆性调节，完成发光淬灭到开启的过程。但是此类材料无法实现从初始发光到另一种颜色发光的转变，这将限制此类材料在信息加密、光电转换、电致发光变色器件上的进一步拓展应用。
发明内容：
本发明的目的在于提供一类基于紫精配体的电刺激响应型铱(Ⅲ)配合物及其应用，微调配合物结构即可实现光颜色的多色变化，且该类材料具有可逆的氧化还原性和良好的循环稳定性，可为电致变色器件、信息存储器件、储能器件的进一步开放提供新思路和新方法。
本发明的技术解决方案为：一类电刺激响应型铱(Ⅲ)配合物，其是在铱(Ⅲ)配合物的C^N配体的苯环或吡啶环的不同位点上修饰乙基吡啶盐单元构建紫精配体，而 N^N配体上引入吸电子的酰胺基团或给电子的甲基后构成，该类配合物的结构通式如下：
其中，C^N配体为下列中任意一个修饰乙基吡啶盐的紫精配体：
进一步地，该类材料上的C^N配体具有可逆氧化还原性质，其与修饰吸电子基或给电子基的N^N配体相互作用，可调控配合物的波长，在电刺激作用下可使材料产生肉眼可见的多色变化。
进一步地，该类化合物在外加电压的作用下具备良好的可逆性和化学稳定性。
利用上述电刺激响应型铱(Ⅲ)配合物制备出电致变色器件后，其通过具有可逆氧化还原性质的C^N配体与修饰吸电子基酰胺基或给电子甲基的N^N配体相互作用，实现材料的多色改变，可用于信息存储。
本发明的有益效果为：
1.本申请公开的电刺激响应型铱(Ⅲ)配合物，是将过渡金属铱(Ⅲ)配合物的发光寿命长、斯托克斯位移大的优点与紫精单元可逆的氧化还原性质结合起来，构建的一类新型电刺激响应型材料；其主要利用紫精结构可逆的氧化还原特性，结合给电子或吸电子基团对配合物电子转移态的影响，在外界刺激(化学刺激或光电刺激)下，改变铱 (Ⅲ)配合物的电子转移态而改变配合物的光物理性质，可实现肉眼可见的光颜色的多彩变化，可应用于信息存储和加密领域；
2.本申请通过在紫精类结构单元的氮原子上引入乙基基团，使得带有乙基紫精配体的铱(Ⅲ)配合物具有良好的氧化还原可逆性和化学稳定性，在电致变色器件、信息存储器件、储能器件中可以有着良好的应用前景；
3.本申请利用过渡金属铱(Ⅲ)配合物对外界刺激的敏感性和高发光量子效率，将外界刺激(如光、电、化学物质等)反射成发光信号发出，便于灵敏检测，可作为高效的新型光电转换、电致变色器件。
附图说明：
图1为过渡金属铱(Ⅲ)配合物Ir-1在加入硼氢化钠前后在乙腈溶液中的发射光谱图；
图2为过渡金属铱(Ⅲ)配合物Ir-2在加入硼氢化钠前后在乙腈溶液中的发射光谱图；
图3为过渡金属铱(Ⅲ)配合物Ir-1和Ir-2在滴定硼氢化钠溶液前在乙腈溶液中的发射光谱图；
图4为过渡金属铱(Ⅲ)配合物Ir-1和Ir-2在滴定硼氢化钠溶液后在乙腈溶液中的发射光谱；
图5为以过渡金属铱(Ⅲ)配合物Ir-1制备的电致变色器件在紫外光激发下的图片；
图6为以过渡金属铱(Ⅲ)配合物Ir-1制备的电致变色器件加电测试之后在紫外光激发下的图片；
图7为以过渡金属铱(Ⅲ)配合物Ir-2制备的电致变色器件在紫外光激发下的图片；
图8为以过渡金属铱(Ⅲ)配合物Ir-2制备的电致变色器件加电测试之后在紫外光激发下的图片；
图9为过渡金属铱(Ⅲ)配合物Ir-1的循环伏安曲线图；
图10为过渡金属铱(Ⅲ)配合物Ir-1的恒流充放电曲线图(50次)；
图11为过渡金属铱(Ⅲ)配合物Ir-2的循环伏安曲线图；
图12为过渡金属铱(Ⅲ)配合物Ir-2的恒流充放电曲线图(50次)。
具体实施方式
为了更好地理解本发明专利的内容，下面通过具体的实施例和附图进一步说明本发明的技术方案，具体包括合成、材料结构表征和光响应过程测试。但这些实例并不限制本发明。在不背离本发明实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
以下实施案例主要是在苯环与吡啶环对位引入对称的乙基吡啶盐构建紫精类C^N配体，C^N配体上引入吸电子基团酰胺基或给电子基团甲基，以配合物Ir-1和配合物Ir-2为例，其结构具体如下所示：
实施例一、配合物Ir-1的制备
具体合成路线如下：
(1)化合物1的制备：取2，5一二溴吡啶(4mmol，940mg)、对溴苯硼酸(4.1mmol，820mg)、碳酸钾(8mmol，1104mg)和四三苯基磷钯(0.2mmol，231mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入20mL甲苯和乙醇的除氧溶液， 85℃下反应24h，冷却至室温，抽滤得溶液，减压蒸馏除去溶剂，再用饱和氯化钠溶液 (50mL)和二氯甲烷(100mL)萃取3次，分离有机相，浓缩溶剂并用柱层析分离得到化合物1；
(2)化合物2的制备：取化合物1(2.1mmol，491mg)和三水合三氯化铱(1mmol，352mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入30mL乙二醇乙醚和10mL水的除氧溶液，110℃下反应24小时后，冷却至室温，抽滤得到固体，依次用去离子水和乙醇清洗3遍，烘干后得到化合物2；
(3)化合物3的制备：取化合物2(0.29mmol，500mg)和自制bpy-dibu(0.59mmol，209mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入20mL二氯甲烷和甲醇的除氧溶液，50℃下反应4小时，冷却至室温，减压蒸馏除去溶剂，柱层析分离法提纯得到化合物3；
(4)化合物4的制备：取化合物3(0.32mmol，500mg)、对吡啶硼酸(1.32mmol，163mg)、四三苯基膦钯(0.06mmol，69mg)和碳酸钾(1.28mmol，176mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，分别注入15mL甲苯和乙醇的除氧溶液，85℃下反应24h，冷却至室温，抽滤得溶液，减压蒸馏除去溶剂，再用饱和氯化钠溶液(50mL)和二氯甲烷(100mL)萃取洗涤3次，分离有机相，减压蒸馏去溶剂，干法上柱，用柱层析分离法得到化合物4；
(5)配合物Ir-1的制备：取化合物4(0.17mmol，200mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，注入1mL碘乙烷和10mL乙腈溶液，在40℃下反应24h，冷却至室温，减压蒸馏除去溶剂，加入饱和的六氟磷酸钾溶液中，常温下搅拌10h，抽滤得到固体配合物Ir-1。
实施例二、配合物Ir-2的制备
具体合成路线如下：
(1)化合物5的制备：取化合物2(0.29mmol，500mg)和4,4'-二甲基-2,2'-联吡啶(0.59mmol，109mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次；分别注入20mL二氯甲烷和甲醇的除氧溶液，55℃下反应5小时，冷却至室温，减压蒸馏除去溶剂，柱层析分离法提纯得到化合物5；
(2)化合物6的制备：取化合物5(0.29mmol，400mg)、对吡啶硼酸(1.20mmol，147mg)、四三苯基膦钯(0.05mmol，58mg)和碳酸钾(1.16mmol，160mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，分别注入15mL甲苯和乙醇的除氧溶液，80℃下反应24h，冷却至室温，抽滤得溶液，减压蒸馏除去溶剂，再用饱和氯化钠溶液(50mL)和二氯甲烷(100mL)萃取洗涤3次，分离有机相，减压蒸馏去溶剂，干法上柱，用柱层析分离法得到化合物6；
(3)配合物Ir-2的制备：取化合物6(0.20mmol，200mg)于双口瓶中，密封反应装置，抽真空，鼓氮气，反复三次，注入1mL碘乙烷和10mL乙腈溶液，在40℃下反应24h，冷却至室温，减压蒸馏除去溶剂，溶解在饱和的六氟磷酸钾的饱和溶液中，常温下搅拌12h，抽滤得到固体化合物Ir-2。
相关性能测试：
1.溶液状态下硼氢化钠滴定还原铱(Ⅲ)配合物实验
(1)配置10μM配合物Ir-1的乙腈溶液，移取2mL于荧光比色皿中，向比色皿中滴加硼氢化钠，测试不加硼氢化钠和滴加硼氢化钠的磷光发射光谱图。如图1所示，测试数据表明：滴加硼氢化钠后，最大发射峰由初始的607nm红移至635nm，发光强度没有明显的变化。
(2)配置10μM配合物Ir-2的乙腈溶液，移取2mL于荧光比色皿中，向比色皿中滴加硼氢化钠，测试不加硼氢化钠和滴加硼氢化钠的磷光发射光谱图。如图2所示，测试数据表明：滴加硼氢化钠后发射光谱有明显的蓝移，由初始的最大发射峰616nm蓝移至552nm。
由此可以看出，在溶液状态下，N^N配体上修饰了酰胺基和甲基后，初始状态时，Ir-1和Ir-2的波长相差不大，但在硼氢化钠溶液刺激之后，二者波长相差甚远，约83nm，这说明二者对波长调控的效果是不同的。Ir-1材料中由于修饰了吸电子基团酰胺基，在化学物质硼氢化钠的刺激下，波长发生明显的红移，而Ir-2材料中由于修饰了给电子基团甲基，在硼氢化钠的刺激下，波长发生明显的蓝移，这些变化都是可以通过肉眼可见的发光颜色变化所观测到的，由此可以看出，该类材料在复合不同基团的情况下，可实现从初始颜色发光到另一种颜色发光的改变，将发光特性不同的具体化合物作用到信息加密领域，并结合乙基紫精配体的氧化还原可逆性，将可构建一类新型依靠波长调控进行信息加密的刺激响应型材料。
2.过渡金属铱(Ⅲ)配合物Ir-1和Ir-2的电致变色器件的制备
将质量比为10:1:15的聚甲基丙烯酸甲酯PMMA(1g)、支持电解质高氯酸锂LiClO4(0.1g)、增塑剂碳酸丙烯酯PC(1.5g)溶于无水乙腈(5mL)，缓慢升温加热直至凝胶化。将铱(Ⅲ)配合物溶于无水乙腈溶液中(浓度：10-4M)，按质量比为3:2的凝胶电解质和配合物的乙腈溶液混合均匀，滴涂在ITO玻璃上，待溶剂自然挥发后，与另一片ITO玻璃重合，利用双面胶进行粘合，密封保护。
上述制备好的电致变色器件在紫外光下器件发光颜色状态如图5和图7所示，发现配合物Ir-1和Ir-2的发光颜色相似，为橙黄光。采用加电装置对器件两端施加2V电压，恒压10s，施加电压之后，器件在紫外光激发下发光颜色如图6和图8所示，以配合物 Ir-1为材料制作的器件发光颜色为橙红光，而以配合物Ir-2为材料制作的器件发光颜色为黄绿光。以上测试结果说明加电测试的结果与采用硼氢化钠还原的结果相符合。
3.铱(Ⅲ)配合物的循环伏安测试与恒流充放电测试
配合物Ir-1和Ir-2的电化学测试采用三电极体系进行测试。工作电极：铂碳电极；参比电极：Ag/AgNO3电极；对电极：铂柱电极；电解质：四丁基六氟磷酸铵的无水乙腈溶液(浓度为0.1M)；CV电位窗口：-2V～2V。1mg的配合物溶于3mL含电解质的无水乙腈中，将三电极置于无水乙腈中，注意保持互不接触且不触碰烧杯底部。用 Ar气除氧5min后，进行测试。
图9和图11分别为配合物Ir-1和配合物Ir-2的循环伏安曲线图，图10和图12分别是配合物Ir-1和配合物Ir-2的恒流充放电曲线图。由所得数据可知，在大约-1V的位置，出现一对可逆的氧化还原峰，可归属于紫精的氧化还原；并且在约-1.5V和+1.5V 处均有一对可逆的氧化还原峰。这些氧化还原峰是完全可逆的，在50个循环的氧化还原恒流充放电后，电位没有变化。以上说明配合物在外加电压下具有良好的可逆性和化学稳定性。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (2)
1.一类电刺激响应型铱(Ⅲ)配合物在电致变色器件、信息存储和加密中的应用，其特征在于，通过具有可逆氧化还原性质的C^N配体与修饰吸电子基或给电子基的N^N配体相互作用，在电刺激作用下使材料产生肉眼可见的多色变化；
该配合物的结构式如下：
2.如权利要求1所述的一类电刺激响应型铱(Ⅲ)配合物在电致变色器件、信息存储和加密中的应用，其特征在于，该配合物在外加电压的作用下具备可逆性和化学稳定性。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110566098.7A CN113278035B (zh) | 2021-05-24 | 2021-05-24 | 一类电刺激响应型铱（ⅲ）配合物及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110566098.7A CN113278035B (zh) | 2021-05-24 | 2021-05-24 | 一类电刺激响应型铱（ⅲ）配合物及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113278035A CN113278035A (zh) | 2021-08-20 |
| CN113278035B true CN113278035B (zh) | 2022-08-26 |
Family
ID=77281194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110566098.7A Active CN113278035B (zh) | 2021-05-24 | 2021-05-24 | 一类电刺激响应型铱（ⅲ）配合物及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113278035B (zh) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283217A (zh) * | 2019-07-24 | 2019-09-27 | 南京邮电大学 | 一种含有紫精单元的磷光寿命响应型铱配合物及其制备方法与应用 |
-
2021
- 2021-05-24 CN CN202110566098.7A patent/CN113278035B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283217A (zh) * | 2019-07-24 | 2019-09-27 | 南京邮电大学 | 一种含有紫精单元的磷光寿命响应型铱配合物及其制备方法与应用 |
Non-Patent Citations (1)
| Title |
|---|
| 新型刺激响应型磷光铱配合物的设计、合成以及性质探究;王俊;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20210215;B014-762页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113278035A (zh) | 2021-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Redox-modulated near-infrared electrochromism, electroluminochromism, and aggregation-induced fluorescence change in an indolo [3, 2-b] carbazole-bridged diamine system | |
| Cárdenas et al. | Synthesis, X-ray structure, and electrochemical and excited-state properties of multicomponent complexes made of a [Ru (tpy) 2] 2+ unit covalently linked to a [2]-catenate moiety. Controlling the energy-transfer direction by changing the catenate metal ion | |
| CN102936494B (zh) | 多功能的自供能电致变色材料的设计与集成的电致变色器件 | |
| Günsel et al. | Ag (I) and Pd (II) sensing, H-or J-aggregation and redox properties of metal-free, manganase (III) and gallium (III) phthalocyanines | |
| Manoharan et al. | Impact of anchoring groups for improving the binding nature of organic dyes toward high efficient dye sensitized solar cells | |
| Yang et al. | Synthesis, spectroscopic characterization, one and two-photon absorption properties, and electrochemistry of truxene π-expanded BODIPYs dyes | |
| Wu et al. | Julolidine dyes with different acceptors and thiophene-conjugation bridge: Design, synthesis and their application in dye-sensitized solar cells | |
| CN110845477A (zh) | 一类新型对称紫精化合物及其制备方法与应用 | |
| Islam et al. | Synthesis and photophysical properties of ruthenium (II) charge transfer sensitizers containing 4, 4′-dicarboxy-2, 2′-biquinoline and 5, 8-dicarboxy-6, 7-dihydro-dibenzo [1, 10]-phenanthroline | |
| Lu et al. | Synthesis, luminescence and excited state absorption properties of conjugated D-π-A and D-π-D phenothiazine compounds | |
| CN104140808A (zh) | 一种含噁唑基吡啶配体的四面体型亚铜配合物发光材料 | |
| Wu et al. | Novel organic dyes based on diarylmethylene-bridged triphenylamine for dye-sensitized solar cells | |
| CN111793062B (zh) | 一类新型非对称紫精化合物及其制备方法与应用 | |
| Huang et al. | Photoactively electroactive polyamide with azo group in the main chain via oxidative coupling polymerization | |
| Mishra et al. | Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru (II) complexes | |
| Liu et al. | Yellow electrochromic polymer materials with fine tuning electrofluorescences by adjusting steric hindrance of side chains | |
| CN110283217B (zh) | 一种含有紫精单元的磷光寿命响应型铱配合物及其制备方法与应用 | |
| Jukes et al. | Photophysical and redox properties of dinuclear ru and os polypyridyl complexes with incorporated photostable spiropyran bridge | |
| Paek et al. | New type of ruthenium sensitizers with a triazole moiety as a bridging group | |
| Deng et al. | Pyrrole-based viologen derivatives with high contrast and magenta color for electrochromic-fluorescent devices | |
| CN104178131B (zh) | 一种含噁唑基吡啶配体的混配型亚铜配合物发光材料 | |
| Wagner et al. | Carbazole-substituted dialkoxybenzodithiophene dyes for efficient light harvesting and the effect of alkoxy tail length | |
| CN113278035B (zh) | 一类电刺激响应型铱（ⅲ）配合物及其应用 | |
| Yildiz et al. | The effect of molecular structure and ultrafast electron injection dynamics on the efficiency of BODIPY sensitized solar cells | |
| Zhuang et al. | Electrochromic/Electrofluorochromic Devices based on Terpyridine‐Attached Viologen Derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |