WO2011152358A1 - Membrane contenant un complexe d'argent - Google Patents

Membrane contenant un complexe d'argent Download PDF

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Publication number
WO2011152358A1
WO2011152358A1 PCT/JP2011/062390 JP2011062390W WO2011152358A1 WO 2011152358 A1 WO2011152358 A1 WO 2011152358A1 JP 2011062390 W JP2011062390 W JP 2011062390W WO 2011152358 A1 WO2011152358 A1 WO 2011152358A1
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group
atom
containing heterocyclic
atoms
carbon atoms
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PCT/JP2011/062390
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Japanese (ja)
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小林　憲史
東村　秀之
敬 開▲高▼
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住友化学株式会社
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    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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    • C07F9/28—Phosphorus compounds with one or more P—C bonds
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    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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    • C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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    • C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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Definitions

  • the present invention relates to a film containing a silver complex.
  • Non-Patent Document 1 As a light emitting material used for an organic electroluminescence element, a phosphorescent light emitting complex using a platinum group metal typified by an iridium complex is considered promising. However, iridium is rare among platinum group metals and is very expensive. For this reason, various types of complexes using inexpensive metals that are advantageous in terms of cost have been studied (Non-Patent Document 1).
  • a film using a known inexpensive metal complex does not have sufficient durability in the presence of oxygen as a luminescent material.
  • an object of the present invention is to provide a film that is cheaper than a platinum group metal complex and uses a complex excellent in durability in the presence of oxygen as a light emitting material.
  • the present invention first provides a film containing a silver complex represented by the following composition formula (1).
  • L 1 is an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion, and a sulfur anion as an atom or ion that can coordinate to Ag +.
  • the total number of atoms and ions that can coordinate to Ag + of L 1 is 3 or more and 6 or less, and one or more of atoms that can coordinate to Ag + of L 1 are L 2 is a molecule having an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion, and a sulfur anion as an atom or ion that can coordinate to Ag +
  • the total number of atoms and ions that can coordinate to Ag + in L 2 is 2.
  • L 3 is a phosphorus atom, nitrogen atom, oxygen atom, as an atom or ion that can coordinate to Ag + Sulfur, arsenic, oxygen Is down and molecules having one atom or ion selected from sulfur anion .
  • X 1 is an anion .a is a number greater than 0.5, b, c and d are the number of independently 0 or is there.)
  • the present invention provides a light emitting device including the film.
  • the present invention provides a silver complex represented by the following composition formula (3).
  • L 4 is A molecule having 4 to 6 phosphorus atoms capable of coordinating to Ag + , or As an atom capable of coordinating to Ag + or as an atom and an ion, it has at least one phosphorus atom and at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion and a sulfur anion.
  • the total number of atoms and ions that can coordinate to Ag + in L 4 is 3 or more and 6 or less.
  • L 5 represents, as capable of coordinating atoms or ions Ag +, phosphorus atom, nitrogen atom, oxygen atom, sulfur atom, arsenic atom, a molecule having an atom or ion selected from oxygen anions and sulfur anions, L 5
  • the total number of atoms and ions capable of coordinating with Ag + is 2.
  • L 6 is a molecule having one atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion, and a sulfur anion as an atom or ion that can coordinate to Ag + .
  • X 2 is an anion.
  • the present invention is a group containing two or more diarylphosphino groups and having one to three hydrogen atoms removed from a nitrogen atom-containing heterocyclic compound, —O ⁇ , —C ( ⁇ O)
  • One or two groups selected from O ⁇ and —S 2 — and in the formula (Aa), (Ab), (Ba ′), (Bb), (Bc), or (Bd) described later Provide the molecule shown.
  • the film of the present invention is cheaper than a film using a platinum group metal complex and has high durability in the presence of oxygen as a light-emitting material. That is, the film of the present invention can exhibit light emission characteristics excellent in sustainability.
  • “optionally substituted” means that a hydrogen atom constituting the compound or group described immediately after it is unsubstituted or a part or all of the hydrogen atoms are substituted with a substituent. Including both.
  • substituent when substituted by a substituent include, unless otherwise specified, a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms.
  • a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms and a hydrocarbyloxy group having 1 to 18 carbon atoms are preferable, and a halogen atom, a hydrocarbyl group having 1 to 12 carbon atoms and a hydrocarbyl having 1 to 12 carbon atoms are preferable.
  • An oxy group is more preferable, a halogen atom and a hydrocarbyl group having 1 to 12 carbon atoms are further preferable, and a halogen atom and a hydrocarbyl group having 1 to 6 carbon atoms are particularly preferable.
  • “which may be substituted” may be rephrased as “which may have a substituent”.
  • Me represents a methyl group
  • n-Bu represents an n-butyl group
  • t-Bu represents a tert-butyl group
  • Ph represents a phenyl group
  • n-Hex represents an n-hexyl group.
  • the film of the present invention contains a silver complex represented by the following composition formula (1).
  • L 1 is a molecule having an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion, and a sulfur anion as an atom / or ion that can coordinate to Ag +
  • the total number of atoms and ions that can be coordinated to Ag + in 1 is 3 or more and 6 or less, and one or more of the atoms that can be coordinated to Ag + in L 1 is a phosphorus atom.
  • L 2 represents an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion and a sulfur anion and / or an ion or an ion that can coordinate to Ag +.
  • the total number of atoms and ions that can coordinate to Ag + of L 2 is two.
  • L 3 is a molecule having one atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion and a sulfur anion as an atom or ion that can coordinate to Ag + .
  • X 1 is an anion.
  • L 1 , L 2 and L 3 are molecules, but each may have a charged functional group. When L 1 , L 2 and L 3 each have a charged functional group, they may be in an ionic state.
  • L 1 has an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion, and a sulfur anion as an atom or ion that can coordinate to Ag +.
  • a phosphorus atom that can coordinate to Ag + is a trivalent phosphorus atom.
  • Examples of the nitrogen atom capable of coordinating to Ag + include a nitrogen atom in an optionally substituted nitrogen-containing heterocyclic compound (coordinable contained in one nitrogen-containing heterocyclic compound) A nitrogen atom is counted as one), and a nitrogen atom in a group obtained by removing one to five hydrogen atoms from an optionally substituted nitrogen-containing heterocyclic compound (the hydrogen atom from the nitrogen-containing heterocyclic compound) A coordinating nitrogen atom contained in one group in which 1 to 5 are removed is counted as 1), a nitrogen atom in an optionally substituted dialkylamino group, an optionally substituted dialkylamino A nitrogen atom in the group, a nitrogen atom in the optionally substituted arylamino group, a nitrogen atom in the optionally substituted alkylarylamino group, a nitrogen atom in the optionally substituted imino group, and Nitrogen in nitrile group Child, and the like.
  • Examples of the oxygen atom that can be coordinated include an oxygen atom to which a hydrogen atom is bonded and an oxygen atom to which a Group 15 element is bonded.
  • Examples of the sulfur atom capable of coordinating to Ag + include a sulfur atom to which a hydrogen atom is bonded, a sulfur atom in an alkyl mercapto group, and a sulfur atom to which a Group 15 element is bonded.
  • Examples of arsenic atoms that can coordinate to Ag + include trivalent arsenic atoms.
  • Examples of the oxygen anion capable of coordinating to Ag + include O ⁇ .
  • Examples of the sulfur anion capable of coordinating with Ag + include S ⁇ .
  • L 1 is a as capable of coordinating atoms to Ag +, may be a molecule having only phosphorus atom three or more than six, capable of coordinating phosphorus atom to Ag + 1 or more, One or more selected from atoms other than phosphorus atoms that can coordinate to Ag + (nitrogen atoms, oxygen atoms, sulfur atoms, and arsenic atoms) and ions that can coordinate to Ag + (oxygen anions and sulfur anions), It may be a molecule having 3 to 6 in total.
  • L 1 includes a molecule having 4 to 6 phosphorus atoms that can coordinate to Ag + .
  • the one of another preferred embodiment of the L 1, and one or more capable of coordinating phosphorus atom to Ag +, Ag + allows coordinating nitrogen atom, Ag + allows coordinating oxygen atom, Ag +
  • a molecule having a total of 3 or more and 6 or less atoms and ions capable of coordination Of the two preferred examples described above, the latter is more preferred.
  • the number of phosphorus atoms capable of coordinating with Ag + contained in L 1 is 1 or more, preferably 2 or more.
  • the durability of the film against oxygen is further improved, so that any of the two or more phosphorus atoms may contain sp 3 carbon atoms.
  • L 1 may have, Ag + allows coordinating phosphorus atom, Ag + allows coordinating nitrogen atom, capable of coordinating oxygen atom to Ag +, capable of coordinating sulfur atom Ag +, the Ag + coordinatable arsenic atom, among which can coordinate sulfur anions to Ag + allows coordinating oxygen anions and Ag +, preferred examples of the non-phosphorus atom is an oxygen anion and sulfur anion, L 1 is an oxygen anion or It is preferable to contain one sulfur anion.
  • the total number of atoms and ions that can coordinate to Ag + in L 1 is 3 or more and 6 or less, and preferably 3 or 4.
  • the atoms and ions that can coordinate to Ag + in L 1 may contain a plurality of the same atoms and ions, or a combination of different atoms and ions. .
  • L 1 is preferably coordinated to Ag +, it is coordinated to Ag + as a monodentate ligand, also coordinated to Ag + as a bidentate ligand, tridentate or more coordination it may be coordinated to Ag + as a child, more preferably coordinated to Ag + as a bidentate or higher ligands, coordinated to Ag + as a tridentate or higher-dentate ligand More preferably.
  • the number of carbon atoms of L 1 is usually 12 to 300, preferably 22 to 250, more preferably 25 to 200, still more preferably 28 to 150, and particularly preferably 30 to 125.
  • L 1 examples include molecules represented by the following formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt), More preferable are the molecules represented by the following formulas (Aa), (Ab), (Ba) to (Bd), and still more preferable are the following formulas (Ba), (Bc) because the complex film-forming property is excellent. ), Particularly preferably a molecule represented by the following formula (Bc).
  • R 11Aa, a R 12Aa, R 13Aa, R 15Aa , R 16Aa, R 17Aa, hydrocarbyl groups R 18Aa and R 21Aa each independently represent a hydrogen atom or an optionally substituted C 1 -C also be ⁇ 50
  • R 14Aa and R 19Aa are each independently of good 1 to 30 carbon atoms optionally substituted alkyl group
  • R 11Aa, R 12Aa, R 13Aa, R 14Aa, R 15Aa, R 16Aa, R 17Aa, R 18Aa, R 19Aa and R21Aa may be the same or different.
  • R 22Aa, R 23Aa, R 25Aa , R 26Aa, R 27Aa and R 28Aa are each independently a hydrogen atom or an optionally substituted C 1 -C also be ⁇ 50 hydrocarbyl group
  • R 24Aa is substituted an alkyl group having a carbon number of 1 ⁇ 30,
  • R 22Aa, R 23Aa, R 24Aa, R 25Aa, R 26Aa, R 27Aa and R 28Aa may be the same or different.
  • R 2Aa is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Aa is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Aa is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • the molecule represented by the formula (Aa) includes an embodiment containing one or more of —P (R 11Aa ) 2 or —P (R 22Aa ) —,
  • R 11Ab is R 12Ab, R 13Ab, R 15Ab , R 16Ab, R 17Ab, hydrocarbyl groups R 18Ab and R 21Ab each independently represent a hydrogen atom or an optionally substituted C 1 -C also be ⁇ 50, R 14Ab and R 19ab are each independently of good 1 to 30 carbon atoms optionally substituted alkyl group, R 11Ab, R 12Ab, R 13Ab, R 14Ab, R 15Ab, R 16Ab, R 17Ab, R 18Ab, R 19Ab and R 21Ab may be the same or different.
  • R 3Ab is a trivalent group having 50 or less carbon atoms.
  • R 11Ba , R 12Ba , R 13Ba , R 15Ba , R 16Ba , R 17Ba , R 18Ba and R 21Ba are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Ba And R 19Ba each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Ba , R 12Ba , R 13Ba , R 14Ba , R 15Ba , R 16Ba , R 17Ba , R 18Ba , R 19Ba and R 21Ba may be the same or different.
  • R 22Ba , R 23Ba , R 25Ba , R 26Ba , R 27Ba and R 28Ba are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Ba may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Ba , R 23Ba , R 24Ba , R 25Ba , R 26Ba , R 27Ba and R 28Ba may be the same or different.
  • R 2Ba is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Ba is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Ba is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • Q 1Ba is —P (R 11Ba ) 2 , a group obtained by removing one hydrogen atom from an optionally substituted nitrogen-containing heterocyclic compound, —O ⁇ , —C ( ⁇ O) O ⁇ , or -S - and it is, Q 2Ba is —P (R 22Ba ) — or a group obtained by removing two hydrogen atoms from an optionally substituted nitrogen atom-containing heterocyclic compound, R 11Ba and R 22Ba are each independently a phenyl group which may be substituted, and R 2Ba may be a direct bond or a group represented by any one of formulas r1 to r12 described later Is, An embodiment is mentioned.
  • R 11Bb , R 12Bb , R 13Bb , R 15Bb , R 16Bb , R 17Bb , R 18Bb and R 21Bb are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Bb And R 19Bb each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Bb , R 12Bb , R 13Bb , R 14Bb , R 15Bb , R 16Bb , R 17Bb , R 18Bb , R 19Bb and R 21Bb may be the same or different.
  • R 22Bb , R 23Bb , R 25Bb , R 26Bb , R 27Bb and R 28Bb are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Bb may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Bb , R 23Bb , R 24Bb , R 25Bb , R 26Bb , R 27Bb and R 28Bb may be the same or different.
  • R 2Bb is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Bb is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Bb is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Bb is a trivalent group having 50 or less carbon atoms.
  • R 11Bc , R 12Bc , R 13Bc , R 15Bc , R 16Bc , R 17Bc , R 18Bc and R 21Bc are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Bc And R 19B each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Bc , R 12Bc , R 13Bc , R 14Bc , R 15Bc , R 16Bc , R 17Bc , R 18Bc , R 19Bc and R 21Bc may be the same or different.
  • R 2Bc is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Bc is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 3Bc is In the case of a group obtained by removing three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • Q 1Bc is —P (R 11Bc ) 2 , a group obtained by removing one hydrogen atom from an optionally substituted nitrogen-containing heterocyclic compound, —O ⁇ , —C ( ⁇ O) O ⁇ , or -S - and it is, Q 3Bc is a group obtained by removing three hydrogen atoms from P or an optionally substituted nitrogen-containing heterocyclic compound;
  • R 11Bc is an optionally substituted phenyl group,
  • R 2Bc is a group represented by any one of formulas r1 to r12 described later, which may be a direct bond or may be substituted; An embodiment is mentioned.
  • R 11Bd , R 12Bd , R 13Bd , R 15Bd , R 16Bd , R 17Bd , R 18Bd and R 21Bd are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Bd And R 19Bd are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Bd , R 12Bd , R 13Bd , R 14Bd , R 15Bd , R 16Bd , R 17Bd , R 18Bd , R 19Bd and R 21Bd may be the same or different.
  • R 4Bd is a tetravalent group having 70 or less carbon atoms.
  • R 11Ca , R 12Ca , R 13Ca , R 15Ca , R 16Ca , R 17Ca , R 18Ca and R 21Ca are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Ca And R 19Ca are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Ca , R 12Ca , R 13Ca , R 14Ca , R 15Ca , R 16Ca , R 17Ca , R 18Ca , R 19Ca and R21Ca may be the same or different.
  • R 22Ca , R 23Ca , R 25Ca , R 26Ca , R 27Ca and R 28Ca are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Ca may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Ca , R 23Ca , R 24Ca , R 25Ca , R 26Ca , R 27Ca and R 28Ca may be the same or different.
  • R 2Ca is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Ca is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Ca is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 11Cb , R 12Cb , R 13Cb , R 15Cb , R 16Cb , R 17Cb , R 18Cb and R 21Cb are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Cb And R 19Cb each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Cb , R 12Cb , R 13Cb , R 14Cb , R 15Cb , R 16Cb , R 17Cb , R 18Cb , R 19Cb and R 21Cb may be the same or different from each other.
  • R 22Cb , R 23Cb , R 25Cb , R 26Cb , R 27Cb and R 28Cb are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Cb may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Cb , R 23Cb , R 24Cb , R 25Cb , R 26Cb , R 27Cb and R 28Cb may be the same or different.
  • R 2Cb is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Cb is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Cb is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Cb is a trivalent group having 50 or less carbon atoms.
  • R 11Cc , R 12Cc , R 13Cc , R 15Cc , R 16Cc , R 17Cc , R 18Cc and R 21Cc are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Cc And R 19Cc each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Cc , R 12Cc , R 13Cc , R 14Cc , R 15Cc , R 16Cc , R 17Cc , R 18Cc , R 19Cc and R 21Cc may be the same or different.
  • R 22Cc , R 23Cc , R 25Cc , R 26Cc , R 27Cc and R 28Cc are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Cc may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Cc , R 23Cc , R 24Cc , R 25Cc , R 26Cc , R 27Cc and R 28Cc may be the same or different.
  • R 2Cc is a divalent group having 50 or less carbon atoms, provided that when the bonded Q 1Cc is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, the bonded Q 2Cc is a nitrogen atom.
  • the group is a group obtained by removing two hydrogen atoms from the containing heterocyclic compound, or when the bonded Q 3Cc is a group obtained by removing three hydrogen atoms from the nitrogen atom-containing heterocyclic compound, a direct bond may be used. .
  • R 11Cd , R 12Cd , R 13Cd , R 15Cd , R 16Cd , R 17Cd , R 18Cd and R 21Cd are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Cd And R 19Cd are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Cd , R 12Cd , R 13Cd , R 14Cd , R 15Cd , R 16Cd , R 17Cd , R 18Cd , R 19Cd and R 21Cd may be the same or different.
  • R 22Cd , R 23Cd , R 25Cd , R 26Cd , R 27Cd and R 28Cd are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Cd may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Cd , R 23Cd , R 24Cd , R 25Cd , R 26Cd , R 27Cd and R 28Cd may be the same or different.
  • R 2Cd is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Cd is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Cd is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Cd is a trivalent group having 50 or less carbon atoms.
  • R 11Ce , R 12Ce , R 13Ce , R 15Ce , R 16Ce , R 17Ce , R 18Ce and R 21Ce are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Ce And R 19Ce are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms,
  • R 11Ce , R 12Ce , R 13Ce , R 14Ce , R 15Ce , R 16Ce , R 17Ce , R 18Ce , R 19Ce and R 21Ce may be the same or different.
  • R 22Ce , R 23Ce , R 25Ce , R 26Ce , R 27Ce and R 28Ce are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Ce may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Ce , R 23Ce , R 24Ce , R 25Ce , R 26Ce , R 27Ce and R 28Ce may be the same or different.
  • R 2Ce is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Ce is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Ce is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 4Ce is a tetravalent group having 70 or less carbon atoms.
  • R 11Cf , R 12Cf , R 13Cf , R 15Cf , R 16Cf , R 17Cf , R 18Cf and R 21Cf are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Cf And R 19Cf each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Cf , R 12Cf , R 13Cf , R 14Cf , R 15Cf , R 16Cf , R 17Cf , R 18Cf , R 19Cf and R21Cf may be the same or different.
  • R 2Cf is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Cf is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 3Cf is In the case of a group obtained by removing three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Cf is a trivalent group having 50 or less carbon atoms.
  • Two or more groups selected from groups in which one or three hydrogen atoms have been removed may be optionally combined to form a ring.
  • R 11Cg , R 12Cg , R 13Cg , R 15Cg , R 16Cg , R 17Cg , R 18Cg and R 21Cg are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Cg And R 19Cg each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Cg , R 12Cg , R 13Cg , R 14Cg , R 15Cg , R 16Cg , R 17Cg , R 18Cg , R 19Cg and R 21Cg may be the same or different.
  • R 22Cg , R 23Cg , R 25Cg , R 26Cg , R 27Cg and R 28Cg are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Cg may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Cg , R 23Cg , R 24Cg , R 25Cg , R 26Cg , R 27Cg and R 28Cg may be the same or different.
  • R 3Cg is a trivalent group having 50 or less carbon atoms.
  • R 11ch is R 12Ch, R 13Ch, R 15Ch , R 16Ch, R 17Ch, hydrocarbyl groups R 18Ch and R 21ch each independently represent a hydrogen atom or an optionally substituted C 1 -C also be ⁇ 50, R 14Ch And R 19Ch are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Ch , R 12Ch , R 13Ch , R 14Ch , R 15Ch , R 16Ch , R 17Ch , R 18Ch , R 19Ch and R 21ch may be the same or different, respectively.
  • Q 4Ch is a tetravalent group having 70 or less carbon atoms that can coordinate to Ag + and includes any one of P, N, O ⁇ or S ⁇ in a nitrogen atom-containing heterocyclic compound. It is.
  • R 2Ch is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Ch is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, and may be a direct bond.
  • Two or more groups selected from a group excluding one hydrogen atom may be optionally combined to form a ring.
  • R 11Ci , R 12Ci , R 13Ci , R 15Ci , R 16Ci , R 17Ci , R 18Ci and R 21Ci are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Ci And R 19Ci is an optionally substituted alkyl group having 1 to 30 carbon atoms, R 11Ci , R 12Ci , R 13Ci , R 14Ci , R 15Ci , R 16Ci , R 17Ci , R 18Ci , R 19Ci and R Each 21Ci may be the same or different.
  • R 5Ci is a pentavalent group having 100 or less carbon atoms.
  • R 11Da , R 12Da , R 13Da , R 15Da , R 16Da , R 17Da , R 18Da and R 21Da are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Da And R 19Da each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Da , R 12Da , R 13Da , R 14Da , R 15Da , R 16Da , R 17Da , R 18Da , R 20Da and R 21Da may be the same or different.
  • R 22Da , R 23Da , R 25Da , R 26Da , R 27Da and R 28Da are each independently a hydrogen atom or a hydrocarbyl group having 1 to 50 carbon atoms which may be substituted, and R 24Da may be substituted It is a good alkyl group having 1 to 30 carbon atoms, and R 22Da , R 23Da , R 24Da , R 25Da , R 26Da , R 27Da and R 28Da may be the same or different.
  • R 2Da is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Da is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Da is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 11Db, a R 12Db, R 13Db, R 15Db , R 16Db, R 17Db, hydrocarbyl groups R 18dB and R 21Db are each independently a hydrogen atom or an optionally substituted C 1 -C also be ⁇ 50, R 14Db and R 19 dB are each independently of good 1 to 30 carbon atoms optionally substituted alkyl group, R 11Db, R 12Db, R 13Db, R 14Db, R 15Db, R 16Db, R 17Db, R 18Db, R 19Db and R 21Db may be the same or different.
  • R 22Db , R 23Db , R 25Db , R 26Db , R 27Db and R 28Db are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Db may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Db , R 23Db , R 24Db , R 25Db , R 26Db , R 27Db and R 28Db may be the same or different.
  • R 2Db is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Db is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Db is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Db is a trivalent group having 50 or less carbon atoms.
  • R 11Dc , R 12Dc , R 13Dc , R 15Dc , R 16Dc , R 17Dc , R 18Dc and R 21Dc are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dc And R 19Dc each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dc , R 12Dc , R 13Dc , R 14Dc , R 15Dc , R 16Dc , R 17Dc , R 18Dc , R 19Dc and R 21Dc may be the same or different.
  • R 22Dc , R 23Dc , R 25Dc , R 26Dc , R 27Dc and R 28Dc are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dc may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Dc , R 23Dc , R 24Dc , R 25Dc , R 26Dc , R 27Dc and R 28Dc may be the same or different.
  • R 2Dc is a divalent group having 50 or less carbon atoms, provided that when bonded Q 1Dc is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, the bonded Q 2Dc is a nitrogen atom.
  • the group is a group obtained by removing two hydrogen atoms from the containing heterocyclic compound, or when the bonded Q 3Dc is a group obtained by removing three hydrogen atoms from the nitrogen atom-containing heterocyclic compound, a direct bond may be used. .
  • R 11Dd , R 12Dd , R 13Dd , R 15Dd , R 16Dd , R 17Dd , R 18Dd and R 21Dd are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dd And R 19Dd each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dd , R 12Dd , R 13Dd , R 14Dd , R 15Dd , R 16Dd , R 17Dd , R 18Dd , R 19Dd and R21Dd may be the same or different.
  • R 22Dd , R 23Dd , R 25Dd , R 26Dd , R 27Dd and R 28Dd are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dd may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Dd , R 23Dd , R 24Dd , R 25Dd , R 26Dd , R 27Dd and R 28Dd may be the same or different.
  • R 2Dd is a divalent group 50 or less carbon atoms, provided that when bound Q 1dd is a nitrogen atom-containing heterocyclic compound from which one hydrogen atom has been removed group or bound Q 2Dd is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 4Dd is a tetravalent group having 70 or less carbon atoms.
  • R 11De , R 12De , R 13De , R 15De , R 16De , R 17De , R 18De and R 21De are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14De And R 19De are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11De and R 12De , R 13De , R 14De , R 15De , R 16De , R 17De , R 18De , R 19De and R21De may be the same or different.
  • R 22De , R 23De , R 25De , R 26De , R 27De and R 28De each independently represent a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24De may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22De , R 23De , R 24De , R 25De , R 26De , R 27De and R 28De may be the same or different.
  • R 2De is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1De is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2De is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3De is a trivalent group having 50 or less carbon atoms.
  • R 11Df , R 12Df , R 13Df , R 15Df , R 16Df , R 17Df , R 18Df and R 21Df are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Df And R 19Df each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Df , R 12Df , R 13Df , R 14Df , R 15Df , R 16Df , R 17Df , R 18Df , R 19Df and R21Df may be the same or different.
  • R 22Df , R 23Df , R 25Df , R 26Df , R 27Df and R 28Df are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Df may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Df , R 23Df , R 24Df , R 25Df , R 26Df , R 27Df and R 28Df may be the same or different.
  • R 2Df is a divalent group having 50 or less carbon atoms, provided that when bonded Q 1Df is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, the bonded Q 2Df is a nitrogen atom.
  • the group is a group obtained by removing two hydrogen atoms from the containing heterocyclic compound, or when the bonded Q 3Df is a group obtained by removing three hydrogen atoms from the nitrogen atom-containing heterocyclic compound, a direct bond may be used. .
  • R 11Dg , R 12Dg , R 13Dg , R 15Dg , R 16Dg , R 17Dg , R 18Dg and R 21Dg are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dg And R 19Dg is an optionally substituted alkyl group having 1 to 30 carbon atoms
  • Each 21Dg may be the same or different.
  • R 22Dg , R 23Dg , R 25Dg , R 26Dg , R 27Dg and R 28Dg are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dg may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Dg , R 23Dg , R 24Dg , R 25Dg , R 26Dg , R 27Dg and R 28Dg may be the same or different.
  • R 2Dg is a divalent group having 50 or less carbon atoms, provided that when bonded Q 1Dg is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, the bonded Q 2Dg is a nitrogen atom.
  • the group is a group obtained by removing two hydrogen atoms from the containing heterocyclic compound, or when the bonded Q 3Dg is a group obtained by removing three hydrogen atoms from the nitrogen atom-containing heterocyclic compound, a direct bond may be used. .
  • R 3Dg is a trivalent group having 50 or less carbon atoms.
  • R 11Dh , R 12Dh , R 13Dh , R 15Dh , R 16Dh , R 17Dh , R 18Dh and R 21Dh are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dh And R 19Dh each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dh , R 12Dh , R 13Dh , R 14Dh , R 15Dh , R 16Dh , R 17Dh , R 18Dh , R 19Dh and R 21Dh may be the same or different.
  • R 22Dh , R 23Dh , R 25Dh , R 26Dh , R 27Dh and R 28Dh are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dh may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Dh , R 23Dh , R 24Dh , R 25Dh , R 26Dh , R 27Dh and R 28Dh may be the same or different.
  • R 2Dh is a divalent group having 50 or less carbon atoms, provided that when bonded Q 1Dh is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, the bonded Q 2Dh is a nitrogen atom.
  • the group is a group obtained by removing two hydrogen atoms from the containing heterocyclic compound, or when the bonded Q 3Dh is a group obtained by removing three hydrogen atoms from the nitrogen atom-containing heterocyclic compound, a direct bond may be used. .
  • R 3Dh is a trivalent group having 50 or less carbon atoms.
  • R 11Di , R 12Di , R 13Di , R 15Di , R 16Di , R 17Di , R 18Di and R 21Di are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Di And R 19Di each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Di , R 12Di , R 13Di , R 14Di , R 15Di , R 16Di , R 17Di , R 18Di , R 19Di and R21Di may be the same or different.
  • R 22Di , R 23Di , R 25Di , R 26Di , R 27Di and R 28Di are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Di may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Di , R 23Di , R 24Di , R 25Di , R 26Di , R 27Di and R 28Di may be the same or different.
  • R 2Di is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Di is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Di is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 4Di is a tetravalent group having 70 or less carbon atoms.
  • R 11Dj , R 12Dj , R 13Dj , R 15Dj , R 16Dj , R 17Dj , R 18Dj and R 21Dj are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dj And R 19Dj each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dj , R 12Dj , R 13Dj , R 14Dj , R 15Dj , R 16Dj , R 17Dj , R 18Dj , R 19Dj and R 21Dj may be the same or different.
  • R 22Dj , R 23Dj , R 25Dj , R 26Dj , R 27Dj and R 28Dj are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dj may be substituted.
  • a good alkyl group having 1 to 30 carbon atoms, and R 22Dj , R 23Dj , R 24Dj , R 25Dj , R 26Dj , R 27Dj and R 28Dj may be the same or different.
  • R 2Dj is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Dj is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Dj is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Dj is a trivalent group having 50 or less carbon atoms.
  • R 11Dk , R 12Dk , R 13Dk , R 15Dk , R 16Dk , R 17Dk , R 18Dk and R 21Dk are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dk And R 19Dk are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dk , R 12Dk , R 13Dk , R 14Dk , R 15Dk , R 16Dk , R 17Dk , R 18Dk , R 19Dk and R 21Dk may be the same or different.
  • R 2Dk is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Dk is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 3Dk is In the case of a group obtained by removing three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 11Dl , R 12Dl , R 13Dl , R 15Dl , R 16Dl , R 17Dl , R 18Dl and R 21Dl are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dl And R 19Dl each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dl , R 12Dl , R 13Dl , R 14Dl , R 15Dl , R 16Dl , R 17Dl , R 18Dl , R 19Dl and R21Dl may be the same or different.
  • R 22Dl, R 23Dl, R 25Dl , R 26Dl, R 27Dl and R 28 dl are each independently a hydrogen atom or an optionally substituted C 1 -C also be ⁇ 50 hydrocarbyl group
  • R 24Dl is substituted an alkyl group having a carbon number of 1 ⁇ 30,
  • R 22Dl, R 23Dl, R 24Dl, R 25Dl, R 26Dl, R 27Dl and R 28 dl may be the same or different.
  • R 2Dl is a divalent group having 50 or less carbon atoms, provided that when Q 1Dl bonded is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, the bonded Q 2Dl is a nitrogen atom.
  • the group is a group obtained by removing two hydrogen atoms from the containing heterocyclic compound, or when the bonded Q 3Dl is a group obtained by removing three hydrogen atoms from the nitrogen atom-containing heterocyclic compound, a direct bond may be used. .
  • R 3Dl is a trivalent group having 50 or less carbon atoms.
  • R 11Dm , R 12Dm , R 13Dm , R 15Dm , R 16Dm , R 17Dm , R 18Dm and R 21Dm are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Dm And R 19Dm each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Dm , R 12Dm , R 13Dm , R 14Dm , R 15Dm , R 16Dm , R 17Dm , R 18Dm , R 19Dm and R21Dm may be the same or different.
  • R 22Dm , R 23Dm , R 25Dm , R 26Dm , R 27Dm and R 28Dm are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dm may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Dm , R 23Dm , R 24Dm , R 25Dm , R 26Dm , R 27Dm and R 28Dm may be the same or different.
  • Q 4Dm is a tetravalent group having 70 or less carbon atoms, which can coordinate to Ag + and contains any one of P, N, O ⁇ or S ⁇ in a nitrogen atom-containing heterocyclic compound. It is.
  • R 2Dm is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Dm is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Dm is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 11Dn , R 12Dn , R 13Dn , R 15Dn , R 16Dn , R 17Dn , R 18Dn and R 21Dn are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dn And R 19Dn each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dn , R 12Dn , R 13Dn , R 14Dn , R 15Dn , R 16Dn , R 17Dn , R 18Dn , R 19Dn and R21Dn may be the same or different.
  • R 2Dn is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Dn is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 3Dn is In the case of a group obtained by removing three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 3Dn is a trivalent group having 50 or less carbon atoms.
  • Two or more groups selected from groups in which one or three hydrogen atoms have been removed may be optionally combined to form a ring.
  • R 11Do , R 12Do , R 13Do , R 15Do , R 16Do , R 17Do , R 18Do and R 21Do are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Do And R 19Do each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Do , R 12Do , R 13Do , R 14Do , R 15Do , R 16Do , R 17Do , R 18Do , R 19Do and R21Do may be the same or different.
  • R 2Do is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Do is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 3Do is In the case of a group obtained by removing three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 4Do is a tetravalent group having 70 or less carbon atoms.
  • R 11Dp , R 12Dp , R 13Dp , R 15Dp , R 16Dp , R 17Dp , R 18Dp and R 21Dp are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Dp And R 19Dp each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Dp , R 12Dp , R 13Dp , R 14Dp , R 15Dp , R 16Dp , R 17Dp , R 18Dp , R 19Dp and R 21Dp may be the same or different.
  • R 22Dp , R 23Dp , R 25Dp , R 26Dp , R 27Dp and R 28Dp each independently represent a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Dp may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Dp , R 23Dp , R 24Dp , R 25Dp , R 26Dp , R 27Dp and R 28Dp may be the same or different.
  • R 3Dp is a trivalent group having 50 or less carbon atoms.
  • R 4Dp is a tetravalent group having 70 or less carbon atoms.
  • R 11Dq , R 12Dq , R 13Dq , R 15Dq , R 16Dq , R 17Dq , R 18Dq and R 21Dq are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Dq And R 19Dq each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Dq , R 12Dq , R 13Dq , R 14Dq , R 15Dq , R 16Dq , R 17Dq , R 18Dq , R 19Dq and R 21Dq may be the same or different.
  • Q 4Dq is a tetravalent group having 70 or less carbon atoms and containing any one of P, N, O ⁇ or S ⁇ in a nitrogen atom-containing heterocyclic compound, which can be coordinated to Ag +. It is.
  • R 2Dq is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Dq is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, and may be a direct bond.
  • R 3Dq is a trivalent group having 50 or less carbon atoms.
  • Two or more groups selected from a group obtained by removing one hydrogen atom from the containing heterocyclic compound may be optionally combined to form a ring.
  • R 11Dr , R 12Dr , R 13Dr , R 15Dr , R 16Dr , R 17Dr , R 18Dr and R 21Dr are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 14Dr And R 19Dr each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms
  • R 11Dr , R 12Dr , R 13Dr , R 14Dr , R 15Dr , R 16Dr , R 17Dr , R 18Dr , R 19Dr and R21Dr may be the same or different.
  • Q 5Dr is a pentavalent group having 100 or less carbon atoms, which can coordinate to Ag + and contains any one of P, N, O ⁇ or S ⁇ in a nitrogen atom-containing heterocyclic compound. It is.
  • R 2Dr is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Dr is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, and may be a direct bond.
  • Two or more groups selected from a group excluding one hydrogen atom may be optionally combined to form a ring.
  • R 11Ds , R 12Ds , R 13Ds , R 15Ds , R 16Ds , R 17Ds , R 18Ds and R 21Ds are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Ds And R 19Ds each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, R 11Ds , R 12Ds , R 13Ds , R 14Ds , R 15Ds , R 16Ds , R 17Ds , R 18Ds , R 19Ds and R21Ds may be the same or different.
  • R 22Ds , R 23Ds , R 25Ds , R 26Ds , R 27Ds and R 28Ds are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 24Ds may be substituted. It is a good alkyl group having 1 to 30 carbon atoms, and R 22Ds , R 23Ds , R 24Ds , R 25Ds , R 26Ds , R 27Ds and R 28Ds may be the same or different.
  • R 2Ds is a divalent group having 50 or less carbon atoms, provided that the bonded Q 1Ds is a group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, or the bonded Q 2Ds is In the case of a group obtained by removing two hydrogen atoms from a nitrogen atom-containing heterocyclic compound, a direct bond may be used.
  • R 5Ds is a pentavalent group having 100 or less carbon atoms.
  • R 11Dt , R 12Dt , R 13Dt , R 15Dt , R 16Dt , R 17Dt , R 18Dt and R 21Dt are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 14Dt And R 19Dt each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, and R 11Dt , R 12Dt , R 13Dt , R 14Dt , R 15Dt , R 16Dt , R 17Dt , R 18Dt , R 19Dt and R 21Dt may be the same or different.
  • R 6Dt is a hexavalent group having 150 or less carbon atoms.
  • R 11Dt , R 12Dt , R 13Dt , R 14Dt , R 15Dt , R 16Dt , R 17Dt , R 18Dt , R 19Dt , R 21Dt , R 6Dt and optionally substituted nitrogen atom-containing heterocyclic compounds A group selected from the groups excluding one may be optionally bonded to form a ring.
  • the molecules represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt) are phosphorus atoms capable of coordinating to Ag +. It is preferable to contain 2 or more. Since the durability of the film against oxygen is improved, it is preferable that the sp 3 carbon atom is not bonded to the phosphorus atom.
  • the structure of the molecule represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt) is A structure having three phosphorus atoms, A structure having two phosphorus atoms and one nitrogen atom, A structure having two phosphorus atoms and one oxygen anion, A structure having two phosphorus atoms and one sulfur anion, or A structure having two phosphorus atoms and one arsenic atom is preferred, A structure having two phosphorus atoms and one nitrogen atom, or A structure having two phosphorus atoms and one oxygen anion is more preferable.
  • the structure of the molecule represented by the above formulas (Ba) to (Bd) is A structure having four phosphorus atoms, A structure having three phosphorus atoms and one nitrogen atom, A structure having three phosphorus atoms and one oxygen anion, A structure having three phosphorus atoms and one sulfur anion, A structure having three phosphorus atoms and one arsenic atom, A structure having two phosphorus atoms and two nitrogen atoms, or A structure having two phosphorus atoms and two arsenic atoms is preferred, A structure having four phosphorus atoms, A structure having three phosphorus atoms and one nitrogen atom, A structure having three phosphorus atoms and one oxygen anion, A structure having three phosphorus atoms and one sulfur anion, or A structure having two phosphorus atoms and two nitrogen atoms is more preferable, A structure having four phosphorus atoms, A structure having three phosphorus atoms and one oxygen anion, or A structure having two
  • the structure of the molecule represented by the above formulas (Ca) to (Ci) is A structure having five phosphorus atoms, A structure having four phosphorus atoms and one nitrogen atom, A structure having four phosphorus atoms and one oxygen anion, A structure having four phosphorus atoms and one sulfur anion, A structure having four phosphorus atoms and one arsenic atom, A structure having three phosphorus atoms and two nitrogen atoms, A structure having three phosphorus atoms and two oxygen atoms, A structure having three phosphorus atoms and two sulfur anions, A structure having three phosphorus atoms and two arsenic atoms, A structure having two phosphorus atoms and three nitrogen atoms, or A structure having two phosphorus atoms and three arsenic atoms is preferred, A structure having five phosphorus atoms, A structure having four phosphorus atoms and one nitrogen atom, A structure having four phosphorus atoms and one oxygen anion, A
  • the structures of the molecules represented by the above formulas (Da) to (Dt) are as follows: A structure having six phosphorus atoms, A structure having five phosphorus atoms and one nitrogen atom, A structure having five phosphorus atoms and one oxygen anion, A structure having five phosphorus atoms and one sulfur anion, A structure having five phosphorus atoms and one arsenic atom, A structure having four phosphorus atoms and two nitrogen atoms, A structure having four phosphorus atoms and two oxygen anions, A structure having four phosphorus atoms and two sulfur anions, A structure having four phosphorus atoms and two arsenic atoms, A structure having three phosphorus atoms and three nitrogen atoms, A structure having three phosphorus atoms and three arsenic atoms, A structure having two phosphorus atoms and four nitrogen atoms, or A structure having two phosphorus atoms and four arsenic atoms is preferred, A structure having six phospho
  • nitrogen-containing heterocyclic compounds in the molecules represented by the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt)
  • pyridine pyridazine, pyrimidine, pyrazine, triazine, quinoline, isoquinoline, imidazole, pyrazole, oxazole, thiazole, oxadiazole, thiadiazole, azadiazole and acridine.
  • pyridine Preferable are pyridine, imidazole, quinoline and isoquinoline, more preferable are pyridine, imidazole and quinoline, and still more preferable are imidazole and quinoline because a complex having good film forming property is easily formed.
  • Examples of the substituent that the nitrogen atom-containing heterocyclic compound may have include a halogen atom, a hydrocarbyl group having 1 to 50 carbon atoms substituted with a halogen atom, a hydrocarbyl group having 1 to 50 carbon atoms, carbon Examples thereof include a hydrocarbyloxy group having 1 to 24 atoms and a diarylamino group having 1 to 24 carbon atoms.
  • the number of substituents that the nitrogen atom-containing heterocyclic compound may have is preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, and particularly preferably 1 to 2. It is a piece.
  • the substituent which the nitrogen atom-containing heterocyclic compound which may be substituted may have may be condensed to form a ring structure.
  • an ethenyl group may be bonded to the 4,5-position of imidazole, and the ethenyl groups may be condensed to form a benzene ring to form a benzimidazole skeleton.
  • hydrocarbyl group which may be substituted in the molecule represented by the formula (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt)
  • hydrocarbyl groups are shown below: Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentadecyl, Alkyl groups having 1 to 50 carbon atoms, such as octadecyl group and docosyl group; A cyclic saturated hydrocarbyl group having 3 to 50 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclodo
  • the hydrocarbyl group is preferably a methyl group, tert-butyl group, hexyl group, dodecyl group, cyclohexyl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 2 -Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group 4-butylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4- (2-ethylhexyl) phenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group, 9 A fluorenyl group or a phenylmethyl
  • Examples of the substituent that the hydrocarbyl group may have are the same as the substituent that the nitrogen atom-containing heterocyclic compound may have, a halogen atom, a hydrocarbyl group having 1 to 50 carbon atoms, and a substituent having 1 to 24 carbon atoms.
  • alkyl group which may be substituted in the molecule represented by the formula (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt).
  • Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, pentadecyl, octadecyl, docosyl, etc.
  • a straight-chain hydrocarbyl group having 1 to 30 carbon atoms which may be an alkyl group having a branched structure such as an isopropyl group, an isobutyl group, a tert-butyl group and a 2-ethylhexyl group.
  • Cyclic structures such as groups, cyclopentyl groups, cyclohexyl groups, cyclononyl groups, cyclododecyl groups, norbornyl groups and adamantyl groups Or an alkyl group having.
  • a methyl group, an ethyl group, a butyl group, a tert-butyl group, a hexyl group, an octyl group, a dodecyl group, an octadecyl group and a cyclohexyl group more preferably a methyl group, a butyl group, a hexyl group and an octyl group. More preferably a methyl group.
  • Examples of the group obtained by removing two hydrogen atoms from the optionally substituted nitrogen atom-containing heterocyclic compound include 2 hydrogen atoms in the above-described example of the optionally substituted nitrogen atom-containing heterocyclic compound. Examples thereof include the same groups as those obtained by removing two hydrogen atoms from the structure of a compound having two or more compounds. Examples of the group obtained by removing three hydrogen atoms from the optionally substituted nitrogen atom-containing heterocyclic compound include 3 hydrogen atoms among the above-described examples of the optionally substituted nitrogen atom-containing heterocyclic compound. Examples thereof include the same groups as those obtained by removing three hydrogen atoms from the structure of a compound having two or more compounds.
  • Examples of the tetravalent group obtained by removing four hydrogen atoms from the optionally substituted nitrogen atom-containing heterocyclic compound include hydrogen among the examples of the optionally substituted nitrogen atom-containing heterocyclic compound. Examples thereof include the same groups as those obtained by removing four hydrogen atoms from the structure of a compound having four or more atoms. Examples of the pentavalent group obtained by removing five hydrogen atoms from the optionally substituted nitrogen atom-containing heterocyclic compound include hydrogen among the examples of the optionally substituted nitrogen atom-containing heterocyclic compound. Examples thereof include the same groups as those obtained by removing five hydrogen atoms from the structure of a compound having 5 or more atoms.
  • Examples of the hexavalent group obtained by removing six hydrogen atoms from the optionally substituted nitrogen atom-containing heterocyclic compound include hydrogen among the examples of the optionally substituted nitrogen atom-containing heterocyclic compound. Examples thereof include the same groups as those obtained by removing six hydrogen atoms from the structure of a compound having 6 or more atoms.
  • a group represented by any one of the following formulas r1 to r12 which may be substituted (for example, a group represented by any one of the following formulas r1 ′ to r12 ′).
  • Y 1 is — (CH 2 ) n —, —O—, —S— , —N (R 50 ) —, —Si (R 51 ) 2 —, —O (CH 2 ) n —, Or a group represented by —O (CH 2 ) n O—
  • Y 2 is — (CH 2 ) n —, —O—, —S—, or —Si (R 51 ) 2 —.
  • N is an integer of 1 to 3.
  • R 50 is an optionally substituted aryl group having 1 to 50 carbon atoms
  • R 51 is an optionally substituted carbon atom. 1 to 50 hydrocarbyl groups.
  • Examples of the aryl group which may be substituted represented by R 50 are phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4 -Methylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butyl Examples include phenyl group, 4-hexylphenyl group, 4- (2-ethylhexyl) phenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group, 4-phenylphenyl group, and 9-fluorenyl group.
  • phenyl group 2-methylphenyl group, 4-methylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 4-tert-butylphenyl group and 4-hexylphenyl group
  • phenyl group 2-methylphenyl group, 2,4,6-trimethylphenyl group and 4-hexylphenyl group
  • phenyl group is a group that is a group.
  • hydrocarbyl group of the optionally substituted hydrocarbyl group represented by R 51 are the formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and Examples of the hydrocarbyl group which may be substituted in the molecule represented by (Da) to (Dt) are the same as those of the hydrocarbyl group.
  • the groups represented by the formulas r1 ′ to r12 ′ that may be substituted which are examples of the groups represented by the formulas r1 to r12 that may be substituted, are shown below.
  • Y 3 is, -CH 2 -, - O - , - S -, - N (R 52) -, or, -Si (R 53) 2 - .
  • R 52 is a group represented by the (It is an aryl group having 1 to 18 carbon atoms which may be substituted, and R 53 is a hydrocarbyl group having 1 to 18 carbon atoms which may be substituted.)
  • Examples of the aryl group having 1 to 18 carbon atoms which may be substituted represented by R 52 and preferred structures thereof include examples of the aryl group which may be substituted and represented by R 50 . Of these, those having 1 to 18 carbon atoms are the same.
  • Examples of the optionally substituted hydrocarbyl group having 1 to 18 carbon atoms represented by R 53 and preferred structures thereof include, among the examples and preferred structures of the hydrocarbyl group represented by R 51 , the number of carbon atoms. Similar to those of 1-18.
  • R 2Xx is preferably a group represented by any one of the aforementioned formulas r1 to r12 which may be substituted, and may optionally be substituted by the formulas r1, r2, r5, r6, r8 And a group represented by any one of r9, a group represented by the formula r10, wherein Y 1 is —O— or —N (R 50 ) —, represented by the formula r11 A group in which Y 1 is —O— or —S—, a group represented by the formula r12, wherein Y 1 is —O—, and Y 2 is —CH 2 - is group, a group represented by the formula r12, a Y 1 in the formula is -O-, Y 2 is -Si (R 51) 2 - group are more preferably, substituted A group represented by any one of the formulas r1 ′, r5 ′, r6 ′ and r10 ′, and
  • Examples of the substituent that the group represented by R 2Xx may have are the formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Da) Dt)
  • a halogen atom a hydrocarbyl group having 1 to 50 carbon atoms, a hydrocarbyloxy group having 1 to 24 carbon atoms, A diarylamino group having 1 to 24 carbon atoms;
  • the number of substituents that the group represented by R 2Xx may have is preferably 0 to 4, more preferably 0 to 3, and still more preferably 0 to 2.
  • the position of the substituent is preferably the following position.
  • r1 ′ preferably one or more selected from 2 ′ and 3 ′; r2 ′: Preferably, one or more selected from 2 ′, 3 ′, 4 ′ and 5 ′, more preferably two of 2 ′ and 5 ′, or two of 3 ′ and 4 ′; r3 ′: Preferably, one or more locations selected from 2 ′, 3 ′, 4 ′, 5 ′, 6 ′ and 8 ′, more preferably, only one location of 4 ′, two locations of 2 ′ and 6 ′, 2 locations 3 ′ and 5 ′, 3 locations 2 ′, 4 ′ and 6 ′, or 3 locations 3 ′, 4 ′ and 5 ′; r4 ′: Preferably, one or more locations selected from 2 ′, 3 ′, 4 ′, 5 ′, 6 ′ and 7 ′, more preferably 2 locations of 2 ′ and 7 ′, 2 of 3 ′ and 6 ′ Or two places, 4 'and 5'; r5
  • R 2xx there is a plurality
  • the group represented by one or more R 2xx Among the groups represented by plural R 2xx is not a direct bond preferable.
  • one or more R 2Ba of the three R 2Ba in the formula (Ba) is preferably not a direct bond
  • molecules of the above formula in this case (Ba) is the following formula (Ba ')
  • Q 1Ba and Q 2Ba are the same as Q 1Ba and Q 2Ba in the formula (Ba).
  • R 3Ab , R 3Bb , R 3Cb , R 3Cd , R 3Cf , R 3Cg , R 3Db , R 3De , R 3Dg , R 3Dh , R 3Dj , R 3Dl , R 3Dn , R 3Dp and R 3Dq (hereinafter referred to as these Examples of the group represented by R 3Xx ) include groups represented by any of the following formulas r31 and r32 which may be substituted.
  • Y 5 , Y 6 and Y 7 are each independently a direct bond or optionally substituted - (CH 2) nm As long as it is not adjacent to each other, any number of CH 2 may be replaced with O, and nm is an integer of 1 to 8.
  • a plurality of Y 5 , Y 6 and Y 7 may be the same or different.
  • R 31 is an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms
  • R 32 is a group represented by any one of the above formulas r1 to r12 which may be directly bonded or substituted.
  • R 33 is an optionally substituted group represented by any one of the above formulas r1 to r12, and the plurality of R 32 and R 33 may be the same or different, and Y 5 , Y 6 , Two or more groups selected from Y 7 , R 31 , R 32 and R 33 are optionally bonded to form a ring. May be.
  • Examples and preferred examples of the hydrocarbyl group of the optionally substituted hydrocarbyl group in R 31 are the formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and ( Examples of the hydrocarbyl group which may be substituted in the molecule represented by Da) to (Dt) and the preferable examples thereof are the same.
  • Examples and preferred examples of the substituent that the hydrocarbyl group may have are also the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and (Da) to (Dt). The examples are the same as the examples and preferred examples of the substituent that the hydrocarbyl group which may be substituted in the molecule represented by
  • R 32 and R 33 are each independently a group represented by any one of the formulas r1 to r12 which may be directly bonded or substituted. Preferably, it is a group represented by any one of the aforementioned formulas r1, r2, r4, r5, r8 and r10 which may be substituted, and more preferably, the formulas r1, r2, r5 and r10 which may be substituted. It is group represented by either.
  • R 32 and R 33 are groups represented by any of the above formulas r1 to r12
  • examples of substituents that the groups represented by the above formulas r1 to r12 may have and preferred examples thereof are the above R 2Xx This is the same as the examples and preferred examples of the substituent that the group represented by
  • R 4Bd, R 4Ce, R 4Dd , R 4Di, R 4Do and R 4DP examples of tetravalent groups represented by (hereinafter, these groups collectively referred to as R 4xx), it may be substituted Examples include the group represented by the following formula r41.
  • Y 8 is C, Si, or, B - a is either Y 9 is a direct bond or - (CH 2) nn -, - O -, - S -, - N (R 60) Or a group represented by —Si (R 61 ) 2 —, nn is an integer of 1 to 3.
  • Two Y 9 s may be the same or different, and R 60 may be substituted.
  • a good aryl group having 1 to 18 carbon atoms, and R 61 is an optionally substituted hydrocarbyl group having 1 to 18 carbon atoms.
  • Examples and preferred examples of the substituent that r41 may have are the same as the examples and preferred examples of the substituent that the group represented by R 2Xx may have.
  • Examples and preferred examples of the aryl group represented by R 60 are the same as those of the aryl group represented by R 52 and preferred examples, respectively.
  • Examples and preferred examples of the hydrocarbyl group represented by R 61 are the same as the examples and preferred examples of the hydrocarbyl group represented by R 53 , respectively.
  • Y 8 and Y 9 of the r41 is preferably a combination Y 8 is located at C 2 both Y 9 are both -O-, Y 8 is located in Si 2 both Y 9 are both -O- combination, the combination Y 8 is located at C 2 both Y 9 are both -S-, combination Y 8 is located in Si 2 both Y 9 are both -S-, and Y 8 is B - a is two A combination in which both Y 9 are —O— is exemplified. A more preferred combination is that Y 8 is Si and the two Y 9 are both —O—.
  • one Q 1Aa is —P (R 11Aa ) 2 ;
  • Q 2Aa is —As (R 23Aa ) — or a group obtained by removing two hydrogen atoms from an optionally substituted nitrogen-containing heterocyclic compound,
  • Combinations R 11Aa, R 12Aa and R 23Aa are each independently a phenyl group which may be substituted; And more preferably
  • One Q 1Aa is —P (R 11Aa ) 2 , —As (R 12Aa ) 2 , a group obtained by removing one hydrogen atom from an optional
  • R 2Aa for each combination of Q 1Aa and Q 2Aa in the formula (Aa) is as described for the group represented by R 2Xx .
  • a preferred combination of Q 1Ab and R 3Ab in the formula (Ab) is:
  • the two Q 1Abs are —P (R 11Ab ) 2 ;
  • R 3Ab is a group represented by any one of the above-described formulas r31 and r32 which may be substituted.
  • a preferred combination of Q 1Ba , Q 2Ba and R 2Ba in the formula (Ba) is:
  • One Q 1Ba is —P (R 11Ba ) 2 or a group obtained by removing one hydrogen atom from an optionally substituted nitrogen-containing heterocyclic compound, and the other Q 1Ba is —O ⁇ .
  • R 2Ba is —P (R 22Ba ) — or a group obtained by removing two hydrogen atoms from an optionally substituted nitrogen atom-containing heterocyclic compound, R 11Ba and R 22Ba are each independently an optionally substituted phenyl group; A combination in which R 2Ba is a direct bond or a group represented by any one of the above formulas r1 to r12 which may be substituted.
  • Q 1Bc , Q 3Bc and R 2Bc in the formula (Bc) is two Q 1Bc are each independently —P (R 11Bc ) 2 , —As (R 12Bc ) 2 , or a group obtained by removing one hydrogen atom from an optionally substituted nitrogen atom-containing heterocyclic compound.
  • Q 1Bc is —O ⁇ , —S ⁇ , —S ( ⁇ O) 2 O ⁇ , or —C ( ⁇ O) O ⁇
  • Q 3Bc is a group obtained by removing three hydrogen atoms from P or an optionally substituted nitrogen-containing heterocyclic compound
  • R 11Bc and R 12Bc are optionally substituted aryl groups, more preferably
  • R 11Bc is an optionally substituted phenyl group, A combination in which R 2Bc is a direct bond or a group represented
  • a preferred combination of Q 1Bd and R 4Bd in the formula (Bd) is Each of the three Q 1Bd groups independently represents —P (R 11Bd ) 2 , —As (R 12Bd ) 2 , or a group obtained by removing one hydrogen atom from an optionally substituted nitrogen-containing heterocyclic compound; And one Q 1Bd is —C ( ⁇ O) O ⁇ , —O ⁇ , —S ⁇ , —S ( ⁇ O) 2 O ⁇ , or —C ( ⁇ O) O ⁇ , (R 11Bd ) and (R 12Bd ) are optionally substituted phenyl groups, In the combination, R 4Bd may be substituted.
  • L 1 examples are represented by the following formulas Aa1 to 94, Ab1 to 4, Ba1 to 20, Bb1, Bc1 to 23, Bd1 to 3, Ca1 to 8, Cc1 to 3, Cf1, Da1 to 4, and Dk1. Molecule.
  • R70 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, An octyl group, a nonyl group, a decyl group, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a tert-butoxy group, or a phenyloxy group.
  • R 71 is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms.
  • R 72 is hydrogen atom, fluorine atom, trifluoromethyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl A group, a decyl group, a methoxy group, or a diphenylamino group.
  • the example of R 73 is the same as the example of R 70 , but R 73 may be directly bonded and connected to R 74 .
  • R 74 is —CH 2 —, and any number may be replaced with O as long as the CH 2 are not adjacent to each other.
  • m is an integer of 1 to 12.
  • the plurality of R 70 to R 74 may be the same or different.
  • Ar 1 is an optionally substituted phenyl group, and a plurality of Ar 1 may be the same or different.
  • Ar 2 is an optionally substituted phenylene group.
  • Y 10 is a group represented by —CH 2 —, —O—, or —S—.
  • Y 11 represents —C (CH 3 ) 2 —, — (CH 2 ) 2 —, —O—, —S—, —Si (CH 3 ) 2 —, —Si (n—C 6 H 13 ) 2 — Or a group represented by —Si (Ph) 2 —.
  • Ph is a phenyl group.
  • the plurality of Y 10 and Y 11 may be the same or different.
  • R 70 is preferably a hydrogen atom, fluorine atom, chlorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, methoxy group, ethoxy group, propyloxy group, butoxy group, a tert-butoxy group or a phenyloxy group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a butyl group, a hexyl group, an octyl group, a methoxy group, a butoxy group, a tert-butoxy group, or A phenyloxy group, more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methoxy group, a butoxy group, a tert-butoxy group, or a phenyloxy group, and particularly preferably a fluor
  • R 71 is preferably a hydrogen atom, phenyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group or dodecyl group, More preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group or a dodecyl group, still more preferably a hydrogen atom, a methyl group, an ethyl group, a butyl group or a hexyl group. And particularly preferably a methyl group.
  • R 72 is preferably a hydrogen atom, a fluorine atom, a trifluoromethyl group, a methyl group, a butyl group, a tert-butyl group, a hexyl group, an octyl group, a methoxy group, or a diphenylamino group, more preferably a hydrogen atom.
  • An atom, a fluorine atom, a trifluoromethyl group, a tert-butyl group, an octyl group or a methoxy group more preferably a hydrogen atom or a fluorine atom.
  • R 73 are the same as the preferred examples of R 70 described above.
  • R 73 may be linked to R 74 by a direct bond.
  • M is preferably an integer of 1 to 10, more preferably an integer of 3 to 10, still more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8.
  • Ar 1 is preferably a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 2-propylphenyl group, 2-isopropylphenyl group, 2-butylphenyl group 2-tert-butylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 3-diphenylaminophenyl group, 4-diphenylaminophenyl group, 3 -Bis (2-methylphenyl) aminophenyl group, 3-bis (4-methylphenyl) aminophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-phenoxyphenyl group, 2 , 6-Dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethyl Phenyl group, 2,6-die
  • Ar 2 is preferably 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 3-methyl-1,2-phenylene group, 4-methyl-1,2-phenylene group, 5-methyl-1,2-phenylene group, 6-methyl-1,2-phenylene group, 6-ethyl-1,2-phenylene group, 6-propyl-1,2-phenylene group, 6-methoxy-1, 2-phenylene group, 6-methyl-1,3-phenylene group, 6-methyl-1,4-phenylene group, 6-methoxy-1,3-phenylene group or 6-fluoro-1,3-phenylene group More preferably, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 6-methyl-1,2-phenylene group, 6-methyl-1,3-phenylene group, 6- Methyl-1,4-phenylene group, 6- Toxi-1,3-phenylene group or 6-fluoro-1,3-phenylene group, more preferably 1,2-phenylene group, 1,3-pheny
  • Y 10 is preferably —CH 2 — or —O—, and more preferably —O—.
  • Y 11 is preferably —C (CH 3 ) 2 —, — (CH 2 ) 2 —, —O—, —Si (CH 3 ) 2 —, —Si (n—C 6 H 13 ) 2 —, or —Si (Ph) 2 —, more preferably —C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, or —Si (Ph) 2 —, particularly preferably —C ( CH 3 ) 2 — and —Si (CH 3 ) 2 —.
  • Z 1 is —O 2 — or —C ( ⁇ O) O 2 — , preferably —O 2 — .
  • Z 2 is —S 2 — or —S ( ⁇ O) 2 O 2 — , preferably —S 2 — .
  • L 1 is preferably a molecule represented by the above formulas Aa1 to 94, Ab1 to 4, Ba1 to 20, Bb1, Bc1 to 23, Bd1 to 3, more preferably the formulas Aa1 to 40 , Aa60 to 66, Aa77 to 80, Aa91 to 94, Ab1 to 4, Ba1 to 16, Ba18 to 20, Bb1, Bc1 to 21, and Bd1 to 3, and more preferably represented by the formulas Aa1 and Aa3 Aa5, Aa13, Aa15, Aa23, Aa24, Aa33, Aa35, Ba1, Ba2, Ba3, Ba6, Ba7, Ba9, Ba11, Ba12, Ba13, Ba14, Ba15, Ba16, Bc1, Bc3, Bc4, Bc5, Bc6, Bc5, Bc6 , Bc8, Bc9, Bc10, Bc14, Bc15, Bc18, Bc19, Bc21, and Bd1 It is a molecule, particularly preferably a molecule represented by the above formula
  • L 1 include the following formulas Aa1 ′, Aa1′-2, Aa3 ′, Aa5 ′, Aa15 ′, Aa23 ′, Aa35 ′, Aa60 ′, Ba1 ′, Ba3 ′, Ba6 ′, Ba11 ′, Ba13 ′. , Ba16 ′, Ba19 ′, Bc1 ′, Bc4 ′, Bc9 ′, Bc15 ′, Bc21 ′, and Bd1 ′.
  • L 1 is preferably represented by the formulas Aa1 ′, Aa1′-2, Aa3 ′, Aa23 ′, Ba1 ′, Ba3 ′, Ba6 ′, Ba11 ′, Ba16 ′, Ba13 ′, Bc4 ′, Bc15.
  • a molecule represented by 'or Bc21' more preferably a molecule represented by the formula Ba3 ', Ba6', Ba11 ', Ba16', Bc4 ', or Bc21'.
  • L 2 in the composition formula (1) has an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion, and a sulfur anion as an atom or ion that can coordinate to Ag +.
  • the total number of atoms and ions that are molecules and can coordinate to Ag + of L 2 is two.
  • L 2 is preferably coordinated to Ag +, be coordinated to Ag + as a monodentate ligand, the Ag + as a bidentate ligand Although it may coordinate, it is more preferable to coordinate to Ag ⁇ +> as a bidentate ligand.
  • the number of carbon atoms of L 2 is usually 2 to 250, preferably 3 to 200, more preferably 4 to 150, still more preferably 6 to 100, and particularly preferably 10 to 80.
  • L 2 is preferably a molecule represented by the following formula (E).
  • R 11E to R 14E are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 50 carbon atoms, and R 16E and R 18E are each independently an optionally substituted carbon atom. different is an alkyl group having 1 to 30, two R 11E, two R 12E, two R 13E, two R 14E, R 16E, and also the two R 18E identical Good .
  • R 2E also be is a divalent group, provided that there two one hydrogen atom from containing heterocyclic compounds a nitrogen atom which may be substituted Q 1E in removing one group In this case, it may be a direct bond selected from R 11E , R 12E , R 13E , R 14E , R 16E , R 18E , R 2E and a group obtained by removing one hydrogen atom from an optionally substituted nitrogen atom-containing heterocyclic ring.
  • the two or more groups selected may be optionally combined to form a ring.
  • hydrocarbyl group and preferred examples of the optionally substituted hydrocarbyl group in R 11E to R 14E are the formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ca)
  • hydrocarbyl group which may be substituted in the molecule represented by Ci) and (Da) to (Dt) and the preferable examples thereof are the same.
  • Examples of the optionally substituted alkyl group in R 16E and R 18E and the substituents that the alkyl group may have and preferred examples thereof include the above formulas (Aa), (Ab), (Ba) to (Bd), ( This is the same as the examples of the alkyl group which may be substituted in the molecule represented by (Ca) to (Ci) and (Da) to (Dt) and the substituent that the alkyl group may have.
  • Examples and preferred examples of the optionally substituted nitrogen-containing heterocyclic compound in Q 1E include the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci), and Examples of the nitrogen atom-containing heterocyclic compound which may be substituted in the molecule represented by (Da) to (Dt) and the examples and preferred examples of the substituent that the nitrogen atom-containing heterocyclic compound may have is there.
  • Examples and preferred examples of the divalent group in R 2E are the same as the examples and preferred examples of the group represented by R 2Xx .
  • the combination of the two Q 1E is preferably two —P (R 11E ) 2, two —As (R 14E ) 2, two groups obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound, O - and -P (R 11E ) 2 one by one, -CO 2 - and -P (R 11E ) 2 one by one, or -S - and -P (R 11E ) 2 one by one Yes, more preferably -P (R 11E ) 2 or two groups obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound.
  • L 2 examples include optionally substituted molecules represented by the following formulas a1 to a37, b1 to b11, c1 to c41, and d1 to d30.
  • L 2 is preferably represented by the formulas a1 to a16, a25 to a37, c1 to c6, c12 to c41, d22.
  • d24 or d26 more preferably represented by the formulas a1 to a2, a4 to a8, a10 to a12, a15 to a16, a25 to a32, c14 to c41, d22, d23, or d26.
  • L 3 is an atom or ion selected from a phosphorus atom, a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion and a sulfur anion as an atom or ion that can coordinate to Ag +.
  • L 3 usually has 2 to 150 carbon atoms, preferably 3 to 100, more preferably 4 to 75, still more preferably 5 to 60, and particularly preferably 6 to 50.
  • L 3 is an optionally substituted nitrogen-containing heterocyclic compound, P (R 11F ) 3 , (P ⁇ O) (R 12F ) 3 , ( P ⁇ S ) (R 13F ) 3 , As (R 14F) 3, R 15F -OH, R 16F -O -, R 17F -CO 2 H, R 18F -CO 2 -, R 19F -SH, R 20F -S -, R 21F -SO 3 H, R 22F - A molecule represented by SO 3 ⁇ or N (R 24F ) 3 is preferred.
  • R 11F to R 22F are each independently a hydrogen atom or an optionally substituted hydrocarbyl group
  • R 24F is an optionally substituted alkyl group having 1 to 30 carbon atoms
  • three R 11F , 3 R 12F , 3 R 13F , 3 R 14F , R 15F , R 16F , R 17F , R 18F , R 19F , R 20F , R 21F , R 22F , and 3 R 24F are the same May be different.
  • Two or more of the three optional of R 11F may form a ring, two or more any of the three R 12F may form a ring, three R 13F the two or more of any of a may be bonded to form a ring, two or more any of the three R 14F may form a ring, three R 24F is bonded to A ring may be formed.
  • Examples and preferred examples of the optionally substituted nitrogen-containing heterocyclic compound as L 3 include the above formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to (Ci). And the examples and preferred examples of the nitrogen atom-containing heterocyclic compound which may be substituted in the molecule represented by (Da) to (Dt).
  • Examples of the hydrocarbyl group which may be substituted in R 11F to R 22F and examples of the substituent which the hydroalkyl group may have and preferred examples thereof are the above formulas (Aa), (Ab), (Ba) to (Bd), respectively. ), (Ca) to (Ci), and (Da) to (Dt) in the molecule represented by the hydrocarbyl group which may be substituted and examples of the substituent that the hydroalkyl group may have and preferred examples It is the same.
  • Examples and preferred examples of the alkyl group which may be substituted in R 24F and the substituent that the alkyl group may have are the formulas (Aa), (Ab), (Ba) to (Bd), (Ca) to Examples of the alkyl group which may be substituted in the molecule represented by (Ci) and (Da) to (Dt) and the substituent which the alkyl group may have and preferred examples thereof are the same.
  • L 3 is preferably an optionally substituted nitrogen-containing heterocyclic compound, P (R 11F ) 3 , R 16F —O ⁇ , R 18F —CO 2 ⁇ , R 20F —S ⁇ , or R 22F
  • a molecule represented by —SO 3 — more preferably an optionally substituted nitrogen-containing heterocyclic compound, P (R 11F ) 3 , R 18F —CO 2 ⁇ , or R 20F —S ⁇ . More preferably, it is a nitrogen atom-containing heterocyclic compound or a molecule represented by P (R 11F ) 3 .
  • L 3 examples include molecules represented by the following formulas e1 to e35 which may be substituted.
  • L 3 is preferably a molecule represented by any one of the formulas e1 to e13, e16 to e20, e25, e26, e28, e32, e33, and e34. More preferably, it is a molecule represented by any of formulas e1 to e13, e16 to e20, e28, and e33.
  • X 1 is an anion, for example, halide ion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), tetrafluoroborate ion, hexa Fluorophosphate ion, hexafluoroantimony ion, hexafluoroarsenic ion, trifluoromethanesulfonate ion, trifluoroacetate ion, tetrakis (pentafluorophenyl) borate ion), sulfate ion, nitrate ion, carbonate ion, acetate ion, Polymerization containing chlorate ion, methanesulfonate ion, benzenesulfonate ion, p-toluenesulfonate ion, dodecylbenzenesulf
  • a is a number greater than 0.5
  • b, c, and d are each independently a number of 0 or more.
  • a value obtained by substituting the a, b, c, and d into the formula (z ⁇ a) + (2 ⁇ b) + c + d is defined as the average coordination number in the composition formula (1).
  • z is the total number of atoms and ions that can coordinate to Ag + in L 1 .
  • the average coordination number is preferably more than 2.0 and 7.0 or less. That is, a, b, c, and d preferably satisfy the following mathematical formula (2). 7.0 ⁇ (z ⁇ a) + (2 ⁇ b) + c + d> 2.0 (2)
  • z is the total number of atoms and ions that can coordinate to Ag + in L 1.
  • the average coordination number in the composition formula (1) is more preferably 3.0 or more and 6.0 or less, further preferably 3.5 or more and 5.5 or less, and 4.0 or more and 5.0. It is particularly preferred that
  • a is preferably a number greater than 0.5 and not greater than 1.5, more preferably a number from 0.6 to 1.4, still more preferably a number from 0.7 to 1.3, The number is preferably 0.8 to 1.2.
  • b is preferably a number from 0 to 1.5, more preferably a number from 0 to 1.0, still more preferably a number from 0 to 0.3 or 1.0, and particularly preferably 0. is there.
  • c is preferably a number of 0 to 1.5, more preferably a number of 0 to 1.0, still more preferably a number of 0 to 0.3 or 1.0, and particularly preferably 0. is there.
  • the number is preferably 0 to 0.3, more preferably 0 to 0.2, still more preferably 0 to 0.1, and particularly preferably 0.
  • Another aspect is preferably a number of 0.5 to 1.5, more preferably a number of 0.6 to 1.5, still more preferably a number of 0.7 to 1.3.
  • the number is preferably 0.8 to 1.2.
  • the aforementioned embodiments are more preferred.
  • the luminescent silver complex in the film of the present invention may be any of a mononuclear complex, a binuclear complex, a trinuclear complex, a tetranuclear complex, a 5-nuclear complex, a hexanuclear complex, and a complex having 7 or more nuclei.
  • it is preferably a mononuclear complex, a binuclear complex, or a trinuclear complex, more preferably a mononuclear complex or a binuclear complex, and still more preferably a mononuclear complex.
  • Examples of silver complexes in the film of the present invention are shown in Table 1-1 and Table 1-2.
  • a, b, c, and d in the composition formula (1) are omitted, an appropriate number as described above can be taken for each compound number.
  • the combinations shown in Table 1-1 and Table 1-2 are preferable, and the Compound Nos. 1 to 9, 31 to More preferred are combinations represented by 41, 72 to 108, and 124 to 154, and further preferred are combinations represented by compound numbers 1 to 9, 31 to 41, 72 to 75, 94 to 100, and 124 to 154. 9, 31-41, 94-100, 124-137 and 148-154 are particularly preferred.
  • Silver complexes represented by the formulas 10 ′, 32 ′, 68 ′, 94 ′, and 95 ′ are representative silver complexes having the combinations represented by the compound numbers 10, 32, 68, 94, and 95, respectively. .
  • the silver complex in the film of the present invention usually exhibits luminescence.
  • the difference between the S1 energy and the T1 energy is preferably 0.3 eV or less, more preferably 0.2 eV or less, and the triplet tends to contribute to light emission, so that it is 0.1 eV or less. Is more preferable. If the difference between the S1 energy and the T1 energy is 0.3 eV or less, a light emission lifetime of 200 ns or more can be exhibited.
  • the structure optimization calculation is performed on the initial structure of the silver complex by density functional theory.
  • B3LYP can be used as the functional
  • LANL2DZ as the silver atom (or Ag + ) and halogen atom as the basis function
  • 6-31G (d) as the other atoms.
  • Gaussian 03 manufactured by Gaussian Inc.
  • none of L 1 , L 2 and L 3 in the composition formula (1) has an anion capable of coordinating to Ag +
  • X 1 is F ⁇ , Cl
  • the total charge is +1
  • at least one of L 1 , L 2 and L 3 has an anion capable of coordinating to Ag +
  • X 1 2 is any one of F ⁇ , Cl ⁇ , Br ⁇ and I ⁇
  • the total charge is 0, and each coordination atom of L 1 , L 2 and L 3 is from a silver atom (or Ag + ) to 3.
  • X 1 is a halide ion
  • the S1 energy here is the energy of the lowest excited singlet state when the ground state is the reference in the one-electron excited state
  • the T1 energy is when the ground state is the reference in the one-electron excited state.
  • the S1 energy and the T1 energy can be obtained by applying a time-dependent density functional method to the optimized structure obtained by the structure optimization calculation and calculating the one-electron excited state.
  • the calculation method used for the time-dependent density functional method can use B3LYP as the functional, Ag + as the basis function, LANL2DZ for the halogen atom, and 6-31G (d) for the other atoms.
  • Gaussian 03 manufactured by Gaussian Inc.
  • the silver complex in the film of the present invention has one or more nitrogen atoms in an optionally substituted nitrogen atom-containing heterocyclic compound as a nitrogen atom capable of coordinating to Ag +
  • L 1 for all of the nitrogen atoms capable of coordinating to Ag + in 1 the distance between the L 1 in Ag + allows coordinating nitrogen atom and Ag + is preferably less than 2.00 ⁇ 3.50 ⁇ . More preferably, it is 2.10 mm or more and 3.40 mm or less, further preferably 2.20 mm or more and 3.30 mm or less, particularly preferably 2.30 mm or more and 3.20 mm or less, and particularly preferably 2.30 mm or more and 2 or less. .70 mm or less.
  • the distance between the Ag + allows coordinating nitrogen atom and Ag + can be determined by a method of performing silver structural optimization calculation by the above density functional method.
  • the silver complex in the film of the present invention can be produced, for example, by a method of mixing a silver salt and a molecule constituting the silver complex in a solvent.
  • the thickness of the film provided by the present invention is usually 1 nm to 50 ⁇ m, preferably 2 nm to 10 ⁇ m, more preferably 3 nm to 5 ⁇ m, still more preferably 5 nm to 3 ⁇ m, and particularly preferably light emission. Since it is easy to flow an electric charge when used in an element, the thickness is 10 nm to 200 nm.
  • the film may contain pinholes or irregularities, but preferably does not contain pinholes or irregularities.
  • the film of the present invention is, for example, a method comprising a step of vapor-depositing a silver complex and other components on a substrate in an arbitrary ratio, or a silver complex and other components suspended in a solvent in an arbitrary ratio or It can be manufactured by a method including a step of dissolving and applying. Preferably, it is produced by a method comprising a step of suspending or dissolving a silver complex and other components in a solvent in an arbitrary ratio and applying the suspension.
  • solvent used in the coating step examples include benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4. -Dioxane, N, N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, methanol, ethanol, isopropyl alcohol, hexane, cyclohexane, and mixtures thereof.
  • Examples of the method for drying the solvent include air drying, heat drying, vacuum drying, heat vacuum drying, and drying performed by blowing nitrogen gas, and air drying or heat drying is preferable, and heat drying is more preferable.
  • Examples of the coating method include spin coating, casting, dip coating, gravure printing, bar coating, roll coating, spray coating, screen printing, flexographic printing, inkjet printing, and offset printing.
  • the spin coating method, casting method, roll coating method, spray coating method, screen printing method, flexographic printing method, ink jet method and offset printing method are preferable.
  • the membrane of the present invention may contain other components.
  • a low-molecular organic material a high-molecular organic material, an organic-inorganic composite material, an inorganic material, and a mixture thereof can be used, and can be arbitrarily selected according to the application.
  • the component include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene.
  • the content of the silver complex in the film is usually 0.01 to 100% by weight, preferably 0.1 to 99% by weight, more preferably 1 to 90% by weight, based on the weight of the whole film. More preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight.
  • the film of the present invention preferably uses a polymer compound as a component for forming the film.
  • the polymer compound include the following. Carbazole derivatives, pyrazoline derivatives, pyrazolone derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, phenylenediamine derivatives, styrylanthracene derivatives, styrylamine derivatives, aromatic dimethylidine derivatives, hydrazone derivatives, polyaromatic tertiary amine compounds, amino A polymer containing a residue of a hole transport material such as a substituted chalcone derivative; Polyarylalkane derivatives, polyvinylcarbazole derivatives, polysilane derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline derivatives, poly (2,5-thienylene vinylene) derivatives, aniline copolymers, polythiophene Polymer hole transport materials such as
  • polycarbazole derivatives polyarylamine derivatives, polyphenylenediamine derivatives, polyhydrazone derivatives, polymers containing residues of polyaromatic tertiary amine compounds, polyarylalkane derivatives, polyvinylcarbazole derivatives, polysilane derivatives, side chains or Polysiloxane derivatives having an aromatic amine structure in the main chain, poly (2,5-thienylene vinylene) derivatives, aniline copolymers, polytriazole derivatives, polyoxadiazole derivatives, polyimidazole derivatives, 8-hydroxyquinoline derivatives Polymers containing residues of the above, polyphthalocyanine derivatives, polymers containing residues of metal porphyrin derivatives, polytriazine derivatives, polyoxazole derivatives, polynaphthalene derivatives, polyaniline derivatives, polythiophene derivatives, polythiophene Nylene vinylene derivative, polyquinoxaline derivative, polymer containing aromatic
  • the number average molecular weight in terms of polystyrene of the polymer compound is usually 1 ⁇ 10 3 to 1 ⁇ 10 8 , preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 , more preferably 2 ⁇ 10 3 to 1. ⁇ 10 6 , more preferably 3 ⁇ 10 3 to 5 ⁇ 10 5 , and particularly preferably 5 ⁇ 10 3 to 1 ⁇ 10 5 .
  • the content of the silver complex in the film is usually 0.01 to 99.99% by weight, preferably 0.1% with respect to the weight of the whole film. It is ⁇ 99% by weight, more preferably 1 to 90% by weight, still more preferably 5 to 80% by weight, and particularly preferably 10 to 50% by weight.
  • the present invention provides a light emitting device containing the film of the present invention.
  • the light-emitting element is usually a light-emitting element in which a pair of electrodes composed of an anode and a cathode and a layer (thin film layer) composed of one or more layers having a light-emitting layer provided between the electrodes are sandwiched.
  • a layer thin film layer
  • the layers is the film of the present invention.
  • the content of the silver complex in the film including the film of the present invention is usually 0.01 to 100% by weight, preferably 0.1 to 99% by weight based on the weight of the whole layer. % By weight, more preferably 1 to 90% by weight, still more preferably 5 to 80% by weight, and particularly preferably 10 to 50% by weight.
  • Examples of the light emitting device of the present invention include a single layer type light emitting device (anode / light emitting layer / cathode) and a multilayer type light emitting device.
  • Examples of the layer configuration of the multilayer light emitting element include the following layer configurations.
  • A anode / hole injection layer / (hole transport layer) / light emitting layer / cathode
  • b anode / light emitting layer / electron injection layer / (electron transport layer) / cathode
  • c anode / hole injection layer / (Hole transport layer) / light emitting layer / electron injection layer / (electron transport layer) / cathode
  • d anode / light emitting layer / (electron transport layer) / electron injection layer / cathode
  • e anode / hole injection layer / (Hole transport layer) / light emitting layer / (electron transport layer) / electron injection layer / cathode
  • any layer constituting the device may be the film of the present invention, and the layer is not limited, but is preferably a light emitting layer.
  • (hole transport layer) and (electron transport layer) represent arbitrary layers that may or may not exist at each position.
  • the anode supplies holes to layers such as a hole injection layer, a hole transport layer, and a light emitting layer, and preferably has a work function of 4.5 eV or more.
  • a metal, an alloy, a metal oxide, an electrically conductive compound, and a combination thereof can be used.
  • Conductive metal oxides metals such as gold, silver, chromium and nickel; mixtures and laminates of the conductive metal oxides and the metals; inorganic conductive materials such as copper iodide and copper sulfide; polyanilines and polythiophenes Examples [polyethylenedioxythiophene and the like], organic conductive materials such as polypyrrole, and a combination thereof with ITO.
  • the cathode supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like.
  • the cathode material for example, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, and a combination thereof can be used.
  • an alkali metal Li, Na, K, Cs, etc.
  • Fluorides and oxides thereof alkaline earth metals (Mg, Ca, Ba, etc.) and fluorides and oxides thereof; gold, silver, lead, aluminum, alloys and mixed metals [sodium-potassium alloys, sodium-potassium mixtures] Metal, lithium-aluminum alloy, lithium-aluminum mixed metal, magnesium-silver alloy, magnesium-silver mixed metal, etc.]; rare earth metal [ytterbium, etc.]; indium;
  • the hole injection layer and the hole transport layer have a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode.
  • materials used for these layers include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted Chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine derivatives, styrylamine derivatives, aromatic dimethylidine derivatives, porphyrin derivatives, polysilane derivatives, poly (N-vinylcarbazole) derivatives , Organosilane derivatives, and polymers
  • the electron injection layer and the electron transport layer have a function of injecting electrons from the cathode, a function of transporting electrons, or a function of blocking holes injected from the anode.
  • materials used for these layers include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives.
  • the electron injection layer and the electron transport layer may have a single layer structure composed of one or more of these, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
  • Inorganic compounds such as insulators and semiconductors can also be used as materials for the electron injection layer and the electron transport layer. If the electron injection layer and the electron transport layer are made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved.
  • insulators include one or more metal compounds selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides, and CaO BaO, SrO, BeO, BaS and CaSe are preferred.
  • Examples of semiconductors include oxides of one or more elements selected from the group consisting of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. , Nitrides and oxynitrides.
  • a reducing dopant may be added to the interface region between the cathode and the film in contact with the cathode.
  • the reducing dopant include alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal. And oxides or rare earth metal halides, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes.
  • the light emitting layer is capable of injecting holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, and has the function of injecting electrons from the cathode, the electron injection layer, or the electron transport layer. It has one of the function of moving electric charges by the force of an electric field and the function of providing a field for recombination of electrons and holes and connecting it to light emission.
  • the silver complex contained in the film of the present invention may be contained in the light emitting layer as a guest material, and further the host material may be contained in the light emitting layer.
  • Examples of the host material include a compound having a fluorene skeleton, a compound having a carbazole skeleton, a compound having a diarylamine skeleton, a compound having a pyridine skeleton, a compound having a pyrazine skeleton, a compound having a triazine skeleton, and a compound having an arylsilane skeleton Is mentioned.
  • the T1 of the host material is preferably larger than that of the guest material, and the difference is more preferably larger than 0.2 eV.
  • the host material may be a low molecular compound or a high molecular compound.
  • the host material may further contain an electrolyte.
  • electrolyte examples include supporting salts (lithium trifluoromethanesulfonate, lithium perchlorate, tetrabutylammonium perchlorate, potassium hexafluorophosphate, tetrafluoroborate. Solvents that may contain tetra-n-butylammonium etc.
  • a light-emitting layer in which a light-emitting material is doped in the host material can be formed by applying a mixture of a host material and a silver complex or by co-evaporation.
  • examples of a method for forming each layer include vacuum deposition methods (resistance heating deposition method, electron beam method, etc.), sputtering methods, LB methods, molecular lamination methods, and coating methods (casting method, spin coating method). , Bar coating method, blade coating method, roll coating method and gravure printing method, screen printing method, ink jet method, etc.), and the coating method is preferable in that the production process can be simplified.
  • the coating method the silver complex, the polymer compound, or a mixture thereof, which is a material of each layer, is mixed with a solvent to prepare a coating solution, and the coating solution is placed on a desired layer (or electrode). It can be formed by coating and drying.
  • the coating solution may contain a resin as a host material and / or a binder. This resin can be dissolved in a solvent or dispersed.
  • a non-conjugated polymer such as polyvinyl carbazole, or a conjugated polymer such as a polyolefin polymer
  • a non-conjugated polymer such as polyvinyl carbazole, or a conjugated polymer such as a polyolefin polymer
  • polyvinyl chloride polycarbonate, polystyrene, polymethyl methacrylate, polybutyl.
  • Methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd Resins, epoxy resins, and silicone resins are listed.
  • the resin solution may further contain an antioxidant, a viscosity modifier and the like.
  • a solvent that uniformly dissolves the components of the film or a solvent that gives a stable dispersion is preferable.
  • alcohols methanol, ethanol, isopropyl alcohol, etc.
  • ketones acetone, methyl ethyl ketone, etc.
  • Chlorinated hydrocarbons chloroform, 1,2-dichloroethane, etc.
  • aromatic hydrocarbons benzene, toluene, xylene, etc.
  • aliphatic hydrocarbons normal hexane, cyclohexane, etc.
  • amides dimethylformamide
  • a high boiling point solvent anisole, bicyclohexylbenzene, etc.
  • the viscosity of the solution is preferably 1 to 100 mPa ⁇ s at 25 ° C.
  • each layer of the light emitting device of the present invention is preferably 0.5 nm to 100 ⁇ m, more preferably 1 nm to 1 ⁇ m.
  • the light emitting device of the present invention can be used for, for example, an illumination light source, a sign light source, a backlight light source, a display device, a printer head, and the like.
  • Examples of the display device include a device of a segment type, a dot matrix type, or the like using a known driving technique, a driving circuit, or the like.
  • the present invention provides a silver complex represented by the following composition formula (3).
  • L 4 is either a molecule having a coordinatable phosphorus atoms four or more than six to Ag +, or, as capable of coordinating atoms to Ag +, or atoms and ions
  • the total number of ions is from 3 to 6.
  • L 5 is a phosphorus atom, nitrogen atom, oxygen atom, sulfur atom, arsenic atom, oxygen anion as an atom or ion that can coordinate to Ag + and a molecule having an atom or ion selected from sulfur anion, .L 6 total number of coordinatable atoms and ions Ag + are two having the L 5 represents, Ag + allows coordinating atoms or As ions, phosphorus atom, nitrogen atom, oxygen atom, sulfur A molecule having one atom or ion selected from a yellow atom, an arsenic atom, an oxygen anion and a sulfur anion, X 2 is an anion, e is a number greater than 0.5, and f, g and h are respectively It is independently a number of 0 or more.)
  • L 4 are the preferred examples and examples of L 1 above. Having 4 or more and 6 or less phosphorus atoms capable of coordinating to Ag + , or As an atom capable of coordinating to Ag + or as an atom and an ion, it has at least one phosphorus atom and at least one selected from a nitrogen atom, an oxygen atom, a sulfur atom, an arsenic atom, an oxygen anion and a sulfur anion.
  • the total number of atoms and ions that can coordinate to Ag + in L 4 is the same as 3 or more and 6 or less.
  • L 5 , L 6 , X 2 , e, f, g and h are the same as L 2 , L 3 , X 1 , a, b, c and d in the composition formula (1), respectively.
  • Preferred examples and examples of L 5 , L 6 , X 2 , e, f, g and h are preferred examples of L 2 , L 3 , X 1 , a, b, c and d in the composition formula (1), respectively. And the same as the example.
  • the present invention is a diaryl phosphino group contains two or more, and, the nitrogen atom-containing heterocyclic one hydrogen atom from the compound to 3 except groups, -O -, and -S - a group selected from A molecule containing one or two and represented by the formula (Aa), (Ab), (Ba ′), (Bb), (Bc) or (Bd) is provided.
  • the molecule of the present invention is useful because it can be used, for example, as a ligand of a metal complex or a reaction catalyst.
  • it is useful as a silver complex contained in the film of the present invention or as a ligand in the silver complex.
  • diarylphosphino group and the nitrogen atom-containing heterocyclic compound examples include —P (R 11Aa ) 2 in the formula Aa, and examples and preferred examples of the nitrogen atom-containing heterocyclic compound, respectively. It is the same.
  • the molecule of the present invention contains two or more diarylphosphino groups and a group obtained by removing one to three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, —O ⁇ , —C ( ⁇ O) O -, or, -S - group 1 or 2 containing a selected from.
  • Two diarylphosphino groups and one group obtained by removing one hydrogen atom from a nitrogen atom-containing heterocyclic compound Diaryl phosphino group two and -O - one, Two diarylphosphino groups and one —C ( ⁇ O) O 2 — , Diaryl phosphino group two and -S - one, Two diarylphosphino groups and two groups obtained by removing one to three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, Three diarylphosphino groups and one group obtained by removing one to three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, Diarylphosphino based on two and nitrogen atom-containing heterocyclic one hydrogen atom from the compound to 3 group remaining after removing one -O - one, Two diarylphosphino groups, one group obtained by removing one to three hydrogen atoms from a nitrogen atom-containing heterocyclic compound, and one —C ( ⁇ O) O 2 — , Dia
  • the molecule of the present invention is a molecule represented by the formula (Aa), (Ab), (Ba ′), (Bb), (Bc) or (Bd).
  • Preferred examples of the molecule of the present invention include the formulas Aa1 to Aa40, Aa77 to Aa80, Aa91 to Aa94, Ba4 to Ba16, Bb1, and Bc6 to Bc21. More preferably, any one of the formulas Aa1 to Aa40, Ba4 to Ba15, Ba21, and Bc6 to Bc18, more preferably any one of the formulas Ba4 to Ba16, and Bc6 to Bc18, and particularly preferably Ba4, Ba6. , Ba8, Ba9, Ba16, and Bc6 to Bc10.
  • the molecule of the present invention preferably has the formula Aa1 ′, Aa1′-2, Aa3 ′, Aa5 ′, Aa15 ′, Aa23 ′, Aa35 ′, Ba6 ′, Ba11 ′, Ba13 ′, Ba16 ′, Bc9 ′, or It is a molecule represented by Bc15 ′.
  • Ba6 ', Ba11', Ba13 ', Ba16', Bc9 ', and Bc15' are more preferable, and formulas Ba6 ', Ba16', and Bc9 'are particularly preferable.
  • a 300 MHz NMR spectrometer manufactured by Varian or a 400 MHz NMR spectrometer manufactured by Burker was used for NMR measurement
  • the AccuTOF TLC (JMS-T100TD) manufactured by JEOL was used for DART-MS measurement.
  • LC908-C60 manufactured by Nippon Analytical Industries, Ltd. and columns JAIGEL-1H-40 and JAIGEL-2H-40 manufactured by Nippon Analytical Industries, Ltd. were used as the developing solvent.
  • An automatic analysis method was used for CHN elemental analysis, a flask combustion-potentiometric titration method was used for Cl elemental analysis, and a flask combustion-ion chromatographic method was used for Br elemental analysis.
  • Aa60 ′ (217 mg, 0.344 mmol) was added to a solution of silver (I) iodide (80.7 mg, 0.344 mmol) in 5 mL of acetonitrile, and the mixture was stirred at 45 ° C. for 30 minutes, and then added with 15 mL of dichloromethane. The mixture was refluxed for 1 hour with stirring. The reaction solution was filtered, the filtrate was concentrated, recrystallized by slow diffusion with chloroform-ether, and the crystals were dried to obtain 297 mg of a pale yellow crystal complex.
  • composition ratio of the obtained complex was determined from the yield, 1 H NMR, 31 P NMR, yield, DART-MS measurement, and elemental analysis value.
  • composition ratio of the obtained complex was determined from 1 H NMR, 31 P NMR, yield, DART-MS measurement, and elemental analysis value.
  • composition ratio of the obtained complex was determined from 1 H NMR, 31 P NMR, yield, DART-MS measurement, and elemental analysis value.
  • Synthesis Example 4 (Compound No. 37 in Table 1-1) To a solution of 13.6 mg of the complex obtained in Synthesis Example 3 in 1.5 mL of dichloromethane was added 2.17 mg (0.0175 mmol) of 1,2,4,5-tetramethylimidazole in 0.5 mL of dichloromethane. Stir for minutes. The reaction solution was concentrated and then vacuum-dried to obtain 15.8 mg of a pale yellow crystal complex.
  • composition ratio of the obtained complex was determined from the mixing ratio.
  • Synthesis Example 5 (Compound No. 36 in Table 1-1) To a solution of 9.85 mg of the complex obtained in Synthesis Example 3 in 1.5 mL of dichloromethane, 2,6-lutidine (1.36 mg, 0.0127 mmol) in 0.5 mL of dichloromethane was added and stirred at 40 ° C. for 10 minutes. The reaction solution was concentrated and then vacuum-dried to obtain 11.2 mg of a pale yellow crystal complex.
  • composition ratio of the obtained complex was determined from the mixing ratio.
  • Example 1 (Synthesis of Aa1 ′) 8-[[o- (Diphenylphosphino) phenyl] phenylphosphino] -quinoline (Aa1 ′) was synthesized by the following method.
  • reaction solution A A 50 mL Schlenk tube was charged with 1-bromo-2-diphenylphosphinobenzene (3.12 g, 9.14 mmol) and 15 mL of dehydrated THF, cooled to ⁇ 65 ° C., and stirred with an n-hexane solution of n-butyllithium ( 1.6 mol / L, 5.5 mL, 8.8 mmol as n-butyllithium) was added dropwise over 5 minutes. The reaction solution turned red was heated to ⁇ 30 ° C. and stirred for 2 hours (reaction solution A).
  • reaction solution B A 50 mL four-necked eggplant-shaped flask was charged with phenyldichlorophosphine (1.58 g, 8.83 mmol) and 8 mL of dehydrated THF, cooled to ⁇ 50 ° C., and the reaction solution A was mixed by sending a cannula. The reaction mixture was gradually warmed to room temperature (23 ° C.) and stirred for 12 hours. The reaction solution became cloudy (reaction solution B).
  • the reaction was gradually warmed to room temperature (23 ° C.) and stirred for 18 hours.
  • Aqueous ammonium chloride solution and chloroform are added to the reaction solution, followed by extraction with chloroform.
  • the obtained organic layer is dried over anhydrous sodium sulfate, filtered and concentrated, and then purified by silica gel column chromatography using chloroform as a developing solvent. This was repeated and dried to obtain 335 mg (yield 7.64%) of Aa1 ′ as a yellow solid.
  • Example 2 (Compound No. 6 in Table 1-1) Aa1 ′ (8.26 mg, 0.0166 mmol) was added to a solution of silver hexafluorophosphate (I) (4.20 mg, 0.0166 mmol) in 1 mL of dichloromethane, and the mixture was stirred at 40 ° C. for 10 minutes. The reaction solution was concentrated and dried to obtain 12.5 mg of an orange solid complex.
  • composition ratio of the obtained complex was determined from the mixing ratio.
  • Example 3 (Compound No. 1 in Table 1-1) Aa1 ′ (12.2 mg, 0.0246 mmol) was added to a solution of silver (I) fluoride (3.12 mg, 0.0246 mmol) in 1 mL of dichloromethane, and the mixture was stirred at 40 ° C. for 10 minutes. The reaction solution was concentrated and dried to obtain 15.3 mg of an orange solid complex.
  • composition ratio of the obtained complex was determined from the mixing ratio.
  • the TFPA solution was added dropwise over 30 minutes while stirring. After stirring at 0 ° C. for 2 hours, a 20 wt% aqueous sodium hydrogen sulfite solution was added to the reaction solution, extraction was performed with dichloromethane, and the obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and water. After concentration of the organic layer, the residue was dissolved in 300 mL of methanol, 1 drop of concentrated hydrochloric acid was added, and the mixture was allowed to stand at room temperature (23 ° C.) for 3 days.
  • TBS-Bc9 'and Bc9' (OH form) were synthesized by the following method.
  • Example 5 (Compound No. 97 in Table 1-2) To a solution of silver (I) bromide (1.90 mg, 0.0101 mmol) in 1 mL of acetonitrile was added Bc9 ′ (OH form) (13.0 mg, 0.0101 mmol), and the mixture was stirred at 45 ° C. for 15 minutes. 0.71 mg, 0.0101 mmol) methanol solution (0.45 mL) was added, and the mixture was stirred at 45 ° C. for 15 minutes. The reaction solution was concentrated, dried and solidified, then added with water, suspended and filtered, and vacuum dried to obtain a colorless solid. 14.1 mg of this complex was obtained.
  • composition ratio of the obtained complex was determined from the CHN elemental analysis value. The results of elemental analysis measurement are shown below.
  • Example 6 (Compound No. 72 in Table 1-1) To a solution of silver tetrafluoroborate (I) (3.72 mg, 0.0191 mmol) in 1 mL of dichloromethane was added 2,2′-6,6′-tetramethoxy-4,4′-bis (di (3,5-xylyl). ) Phosphino) -3,3′-bipyridine (Ba19 ′) (14.5 mg, 0.0191 mmol) was added, and the mixture was stirred at room temperature (23 ° C.) for 10 minutes. 2,9-Dichloro-1,10-phenanthroline (4.76 mg, 0.0191 mmol) was added to the reaction solution, and the mixture was stirred at 40 ° C. for 10 minutes. The reaction solution was concentrated and then vacuum dried to obtain 22.9 mg of a pale yellow crystal complex.
  • composition of the obtained complex was determined from the mixing ratio.
  • Example 21 (Synthesis of Aa3 ′) Aa3 ′ was synthesized by the following method. N-methyl-2- (2-bromophenyl) benzimidazole was prepared according to Org. Biomol. Chem. 3297-3302 (2006). A 50 mL Schlenk tube is charged with 1-bromo-2-diphenylphosphinobenzene (2.93 g, 8.59 mmol) and 15 mL of dehydrated THF, cooled to ⁇ 65 ° C., and stirred with an n-hexane solution of n-butyllithium. (1.6 mol / L, 5.5 mL, 8.8 mmol as n-butyllithium) was added dropwise over 5 minutes.
  • reaction solution D The reaction solution turned red was heated to ⁇ 35 ° C. and stirred for 1 hour (reaction solution D).
  • a 50 mL eggplant-shaped flask was charged with phenyldichlorophosphine (1.57 g, 8.77 mmol) and 8 mL of dehydrated THF, cooled to ⁇ 65 ° C., and the reaction solution D was mixed by sending a cannula.
  • the reaction solution was stirred for 12 hours while gradually warming to room temperature (23 ° C.). As a result, the reaction solution became cloudy (reaction solution E).
  • reaction solution F was stirred overnight while gradually warming to room temperature (23 ° C.), and then stirred at 50 ° C. for 1 hour.
  • Aqueous ammonium chloride solution and chloroform were added to the reaction solution, followed by extraction with chloroform.
  • the organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and then subjected to colorless solid diphosphine 2 by preparative GPC. 675 mg (yield 12.9%) of an oxide was obtained.
  • the diphosphine dioxide (500 mg, 0.822 mmol) synthesized above, 3.94 g of triethylamine and 10 mL of dehydrated xylene were added to a 100 mL four-necked flask, cooled to 0 ° C., and trichlorosilane (5 0.000 g, 37.0 mmol) was added dropwise over 10 minutes. After returning to room temperature (23 ° C.) by natural temperature rise, the mixture was stirred at 130 ° C. for 12 hours. The reaction solution was returned to room temperature (23 ° C.), and 5 mL of a 30 wt% aqueous sodium hydroxide solution was added dropwise, followed by extraction with xylene. The organic layer was concentrated, dried and solidified. The residue was subjected to silica gel column chromatography using a developing solvent chloroform to obtain 202 mg (yield 47.3%) of colorless solid Aa3 '.
  • Example 22 (Compound No. 13 in Table 1-1) Aa3 ′ (6.63 mg, 0.0115 mmol) was added to a suspension of silver (I) iodide (2.70 mg, 0.0115 mmol) in 0.5 mL of acetonitrile, and the mixture was stirred for 3 minutes. For 5 minutes. The reaction solution was concentrated and dried to obtain 9.33 mg of a solid complex.
  • composition of the obtained complex was determined from the mixing ratio.
  • Example 23 (Compound No. 11 in Table 1-1) To a suspension of silver chloride (I) (2.10 mg, 0.0147 mmol) in 0.5 mL of acetonitrile, Aa3 ′ (8.45 mg, 0.0147 mmol) was added and stirred for 3 minutes, and then 1 mL of dichloromethane was added at 40 ° C. Stir for 5 minutes. The reaction solution was concentrated and dried to obtain 10.6 mg of a solid complex.
  • composition of the obtained complex was determined from the mixing ratio.
  • Example 24 (Compound No. 124 in Table 1-3) Aa3 ′ (6.52 mg, 0.0113 mmol) was added to a 1.5 mL suspension of silver tetrafluoroborate (I) (2.20 mg, 0.0113 mmol) in dichloromethane, and the mixture was stirred at 40 ° C. for 5 minutes. The reaction solution was concentrated and dried to obtain 8.72 mg of a solid complex.
  • composition of the obtained complex was determined from the mixing ratio.
  • Example 25 (synthesis of Aa1′-2 and Ba16 ′) A crude product containing Ba16 ′ was synthesized by the following method, and 8-[[o- (diphenylphosphino) phenyl] phenylphosphino] -2-methylquinoline (Aa1′-2) was synthesized by the following method. .
  • Example 26 (Compound No. 132 in Table 1-3) Aa1′-2 (15.9 mg, 0.0311 mmol) was added to a 2.0 mL chloroform suspension of silver (I) iodide (7.30 mg, 0.0311 mmol), and the mixture was stirred at 40 ° C. for 5 minutes. The reaction solution was concentrated and dried to obtain 23.2 mg of a solid complex.
  • composition of the obtained complex was determined from the mixing ratio.
  • Example 27 (Compound No. 133 in Table 1-3) Aa1′-2 (14.7 mg, 0.0288 mmol) was added to a suspension of silver tetrafluoroborate (I) (5.60 mg, 0.0288 mmol) in 2 mL of dichloromethane, and the mixture was stirred at 40 ° C. for 5 minutes. The reaction solution was concentrated and dried to obtain 20.3 mg of a solid complex.
  • composition of the obtained complex was determined from the mixing ratio.
  • NMR data of the complex is shown below. NMR spectra were obtained from Chem. Commun. Since the pattern was the same as the complex described in 6384-6386 (2008), it was a complex having the structure shown above.
  • Solid emission quantum efficiency The solid emission quantum efficiency under air at room temperature (23 ° C.) was measured with a quantum efficiency measurement device (manufactured by Sumitomo Heavy Industries Mechatronics) as follows. Sample preparation was performed as follows. Approximately 1.5 mg of a sample composed only of the complex synthesized in the above examples and comparative examples was sandwiched between two quartz plates of 18 mm square and 0.3 mm thickness at room temperature (23 ° C.), and pressed to 10 mm ⁇ It was stretched to an ellipse of about 5 mm, and the four sides were fixed with tape and sealed.
  • the equipment configuration is as follows.
  • the light source was a Class 3B He-Cd CW laser manufactured by Kimmon.
  • An ND filter FDU0.5 manufactured by OFR was inserted into the emission part and led to an integrating sphere with an optical fiber.
  • a model 2400 source meter manufactured by KEYTHLEY was connected via an integrating sphere, polychromator, and CCD multichannel detector manufactured by Sumitomo Heavy Industries Mechatronics, and data was captured by a notebook PC.
  • the measurement procedure was as follows. Place the sample prepared under the above conditions in an integrating sphere in room temperature (23 ° C) air, set the laser excitation light to 325 nm, CW light, integration time 300 ms, excitation light integration range 315 to 335 nm, PL wavelength integration The range was 390 to 800 nm.
  • the quantum efficiency was calculated according to the procedure of measurement / analysis software manufactured by Sumitomo Heavy Industries Mechatronics.
  • Solid emission wavelength A sample prepared by the same method as the solid emission quantum efficiency measurement is set in a sample fixing place of a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, Fluorolog-Tau3), and the excitation wavelength is 350 nm and solid emission is performed. The wavelength was measured.
  • Solid emission lifetime Measurement and analysis were performed as follows. A sample prepared by the same method as the solid-state luminescence quantum efficiency measurement is set in a sample fixing place for an unknown sample of a fluorescence spectrophotometer (manufactured by JOBINYVON-SPEX, Inc., Fluorolog-Tau3).
  • the structure optimization calculation was performed using the density functional method of the Gaussian 03 program (revision D.02, manufactured by Gaussian Inc.).
  • a one-electron excited state was calculated using a time-dependent density functional method, similarly using the Gaussian 03 program.
  • the functionals are B3LYP, basis functions are Ag + and LANL2DZ for halogen atoms, and 6-31G (d) for other atoms.
  • the complex had an S1 energy of 3.07 eV, a T1 energy of 3.01 eV, and a difference between the S1 energy and the T1 energy was 0.06 eV.
  • Example 2 As a model of the complex obtained in Example 5, 1 atom of silver atom and 1 molecule of Bc9 ′ were used. As an initial configuration, three phosphorus atoms capable of coordinating to Ag + contained in Bc9 ′ and one oxygen anion are all placed within a distance of 3.0 cm or less from the silver atom (structure of compound 95 ′), and Gaussian03 Structure optimization calculations were performed using the density functional theory of the program (Revision D.02, manufactured by Gaussian Inc.). For the optimized structure obtained, a one-electron excited state was calculated using a time-dependent density functional method, similarly using the Gaussian 03 program.
  • the functional method is B3LYP
  • the basis function is Ag + and LANL2DZ for halogen atoms
  • 6-31G (d) for other atoms.
  • the complex had an S1 energy of 2.61 eV, a T1 energy of 2.61 eV, and a difference between the S1 energy and the T1 energy was 0.00 eV.
  • Example 3 As a model of the complex obtained in Example 6, a structure was used in which one atom of silver, one molecule of Ba19 ′, one molecule of 2,9-dichloro-1,10-phenanthroline, and no counter ions were used. . Two phosphorus atoms capable of coordinating to Ag + contained in Ba19 ′ as an initial configuration and two nitrogen atoms capable of coordinating to Ag + contained in 2,9-dichloro-1,10-phenanthroline All of them were installed within a distance of 3.0 cm from the silver atom, and the structure optimization calculation was performed using the density functional method of the Gaussian 03 program (Revision D.02, manufactured by Gaussian Inc.).
  • a one-electron excited state was calculated using a time-dependent density functional method, similarly using the Gaussian 03 program.
  • the functional method is B3LYP
  • the basis function is Ag + and LANL2DZ for halogen atoms
  • 6-31G (d) for other atoms.
  • the complex had an S1 energy of 2.29 eV, a T1 energy of 2.29 eV, and a difference between the S1 energy and the T1 energy was 0.00 eV.
  • Example 4 As a model of the complex obtained in Example 22, one silver atom, one Aa3 ′ molecule, and one iodine atom were used. As an initial configuration, two phosphorus atoms capable of coordinating to Ag + contained in Aa3 ′, one nitrogen atom capable of coordinating to Ag + contained in Aa3 ′, and one iodine atom all from silver atoms Installation was performed at a distance of 3.0 mm or less, and the structure optimization calculation was performed using the density functional method of the Gaussian 03 program (revision D.02, manufactured by Gaussian Inc.). For the optimized structure obtained, a one-electron excited state was calculated using a time-dependent density functional method, similarly using the Gaussian 03 program.
  • the functionals are B3LYP, basis functions are Ag + and LANL2DZ for halogen atoms, and 6-31G (d) for other atoms.
  • the complex had an S1 energy of 2.81 eV, a T1 energy of 2.78 eV, and a difference between the S1 energy and the T1 energy was 0.03 eV.
  • the distance between silver and the nitrogen atom coordinated with silver was 2.54 cm.
  • Example 5 As a model of the complex obtained in Example 26, 1 atom of silver atom, 1 molecule of 8-[[o- (diphenylphosphino) phenyl] phenylphosphino] -2-methylquinoline (Aa1′-2), iodine atom One atom was used.
  • the functional is B3LYP
  • the basis function is LANL2DZ for silver and halogen atoms
  • 6-31G (d) for other atoms.
  • the complex had an S1 energy of 2.54 eV, a T1 energy of 2.47 eV, and a difference between the S1 energy and the T1 energy was 0.07 eV.
  • the distance between silver and the nitrogen atom coordinated with silver was 3.12 cm.
  • a spin coater manufactured by Oshibell Co., Ltd., SC-150
  • a spin coater manufactured by Oshibell Co., Ltd., SC-150
  • 1,2-dichloroethane 2: 1 weight ratio
  • a spin coater manufactured by Oshibell Co., Ltd., SC-150
  • the thicknesses of the thin films using the complexes of Examples 2, 3, 5, 6, 26, and 27 were 0.98 ⁇ m, 1.2 ⁇ m, 2.8 ⁇ m, 2.3 ⁇ m, 1.7 ⁇ m, and 1.7 ⁇ m, respectively. Met.
  • the thin film is placed in the integrating sphere of a quantum efficiency measurement device (manufactured by Sumitomo Heavy Industries Mechatronics Co., Ltd.). The efficiency was measured, and the value obtained by dividing the difference in the decay rate of the emission quantum efficiency before and after the laser light irradiation by the elapsed time was determined as the oxygen deterioration rate. Similarly, the value obtained by measuring the emission quantum efficiency in about 5 seconds after laser light irradiation in a nitrogen atmosphere was defined as the thin film emission quantum efficiency. The results are shown in Table 3.
  • poly (ethylenedioxythiophene) / polystyrene sulfonic acid manufactured by Bayer, trade name: Bytron P AI4083
  • the film was formed by spin coating for 60 seconds and dried at 130 ° C. for 10 minutes. Then, about 3 nm of lithium fluoride and then about 80 nm of aluminum were vapor-deposited as a cathode, and the light emitting element was produced. By applying a voltage of 18 V to the obtained device, yellow light emission with a luminance of 42 cd / m 2 and an efficiency of 1.0 cd / A was confirmed.

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Abstract

L'invention porte sur une membrane utilisant un complexe d'argent, qui est économique par comparaison avec un complexe à base d'un métal du groupe du platine, et qui présente une excellente durabilité en présence d'oxygène quand elle est utilisée en tant que matériau électroluminescent. Plus précisément, elle porte sur une membrane contenant un complexe d'argent représenté par la formule de composition ci-après (1) : (Ag+)(L1)a(L2)b(L3)c(X1)d. (L1 représente une molécule ayant en tout 3 à 6 des atomes et/ou ions suivants : au moins un atome de phosphore et au moins un atome d'azote, atome d'oxygène, atome de soufre, atome d'arsenic, anion oxygène et/ou anion soufre. L² représente une molécule ayant en tout deux atomes et/ou ions choisis parmi les atomes et ions mentionnés ci-dessus. L3 représente une molécule ayant l'un des atomes ou ions mentionnés ci-dessus. X1 représente un anion, a représente un nombre supérieur à 0,5, et b, c et d représentent chacun indépendamment des autres un nombre supérieur ou égal à 0).
PCT/JP2011/062390 2010-05-31 2011-05-30 Membrane contenant un complexe d'argent WO2011152358A1 (fr)

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JP2013229425A (ja) * 2012-04-25 2013-11-07 Sumitomo Chemical Co Ltd 発光素子、並びに、銀錯体および該銀錯体を含有する素子用インク
CN106366126A (zh) * 2015-07-23 2017-02-01 赢创德固赛有限公司 用于烷氧基羰基化的基于苯的二膦配体
CN114591365A (zh) * 2022-03-22 2022-06-07 郑州大学 一种基于苯并咪唑膦氧配体的发光铜化合物及其制备方法和应用

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WO2012144530A1 (fr) * 2011-04-22 2012-10-26 住友化学株式会社 Complexe de cuivre
JP2013229425A (ja) * 2012-04-25 2013-11-07 Sumitomo Chemical Co Ltd 発光素子、並びに、銀錯体および該銀錯体を含有する素子用インク
CN106366126A (zh) * 2015-07-23 2017-02-01 赢创德固赛有限公司 用于烷氧基羰基化的基于苯的二膦配体
EP3121184A3 (fr) * 2015-07-23 2017-02-08 Evonik Degussa GmbH Ligands de disphosphine à base de benzol pour l'alkoxy-carbonylation
US9725398B2 (en) 2015-07-23 2017-08-08 Evonik Degussa Gmbh Benzene-based diphosphine ligands for alkoxycarbonylation
CN106366126B (zh) * 2015-07-23 2019-09-27 赢创德固赛有限公司 用于烷氧基羰基化的基于苯的二膦配体
CN114591365A (zh) * 2022-03-22 2022-06-07 郑州大学 一种基于苯并咪唑膦氧配体的发光铜化合物及其制备方法和应用
CN114591365B (zh) * 2022-03-22 2023-09-05 郑州大学 一种基于苯并咪唑膦氧配体的发光铜化合物及其制备方法和应用

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