Structure, Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers

Dmitry E. Royzman; Andrew M. Noviello; Kylie M. Henline; Robert D. Pike; James P. Killarney; Howard H. Patterson; Carlos Crawford; Zerihun Assefa

doi:10.1007/s10904-013-9978-7

Structure, Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers

Dmitry E. Royzman
, Andrew M. Noviello
, Kylie M. Henline
, Robert D. Pike
, James P. Killarney
, Howard H. Patterson
, Carlos Crawford
, Zerihun Assefa

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The dimeric complex of Cu(I) [Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(MeCN)<inf>2</inf>(Bpy)](BF<inf>4</inf>)<inf>2</inf> (1a, Bpy = 4,4′-dipyridyl) self-assembles in CH<inf>2</inf>Cl<inf>2</inf> or acetone and shows intense photoluminescence (excitation λ<inf>max</inf> = 356 nm, emission λ<inf>max</inf> = 486 nm, ϕ = 0.47). The MeCN ligands are readily removed from 1a, producing [Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(Bpy)](BF<inf>4</inf>)<inf>2</inf> (1b) and altering the photophysical behavior (excitation λ<inf>max</inf> = 336 nm, emission λ<inf>max</inf> = 568 nm, ϕ = 0.07). The desolvated compound 1b reversibly absorbs many vapor phase nucleophiles, as revealed by thermogravimetry. Intense luminescence emission is restored for 1b/Nu, Nu = MeCN (1a), acetone, tetrahydrothiophene (THT), and Et<inf>2</inf>S. Films of 1b are produced when CH<inf>2</inf>Cl<inf>2</inf> solutions of 1a are cast onto glass. The films also react with Nu vapor, again producing intense emission. The pyrazine-bridged dimer [Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(MeCN)<inf>2</inf>(Pyz)](BF<inf>4</inf>)<inf>2</inf> (2a) is produced in CH<inf>2</inf>Cl<inf>2</inf>, while [Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(MeCN)(acetone)(Pyz)](BF<inf>4</inf>)<inf>2</inf>∙½[Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(MeCN)<inf>2</inf>(Pyz)](BF<inf>4</inf>)<inf>2</inf> (2b) is formed in acetone. The crystal structure of the polymer {[Cu(PPh<inf>3</inf>)<inf>2</inf>(Bpy)](BF<inf>4</inf>)∙acetone}<inf>n</inf> (3) is reported, as is the mixed polymer/dimer structure {[Cu(PPh<inf>3</inf>)<inf>2</inf>(Pyz)](BF<inf>4</inf>)}<inf>n</inf>∙½n[Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(BF<inf>4</inf>)<inf>2</inf>(Pyz)] (4b) in which the dimer units show Cu–FBF<inf>3</inf> coordination. The Pyz dimer and the Pyz and Bpy polymers show much weaker luminescence behavior than that of Bpy dimers 1a and the related 1b/Nu adducts. Nucleophile adduct structures [Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(THT)<inf>2</inf>(Bpy)](BF<inf>4</inf>)<inf>2</inf>∙½ethyl ether (5) and [Cu<inf>2</inf>(PPh<inf>3</inf>)<inf>4</inf>(Py)<inf>2</inf>(Bpy)](BF<inf>4</inf>)<inf>2</inf>∙CH<inf>2</inf>Cl<inf>2</inf> (6) confirmed the coordination of one Nu per Cu to 1b.

Original language	English
Pages (from-to)	66-77
Number of pages	12
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	24
Issue number	1
DOIs	https://doi.org/10.1007/s10904-013-9978-7
State	Published - Jan 1 2014

Keywords

Copper
Luminescence
Metal complex film
Metal–organic dimer
Metal–organic polymer
Nucleophile
X-ray crystal structure

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10.1007/s10904-013-9978-7

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@article{34be5aee76794c2d95c6f693f782e34d,

title = "Structure, Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers",

abstract = "The dimeric complex of Cu(I) [Cu2(PPh3)4(MeCN)2(Bpy)](BF4)2 (1a, Bpy = 4,4′-dipyridyl) self-assembles in CH2Cl2 or acetone and shows intense photoluminescence (excitation λmax = 356 nm, emission λmax = 486 nm, ϕ = 0.47). The MeCN ligands are readily removed from 1a, producing [Cu2(PPh3)4(Bpy)](BF4)2 (1b) and altering the photophysical behavior (excitation λmax = 336 nm, emission λmax = 568 nm, ϕ = 0.07). The desolvated compound 1b reversibly absorbs many vapor phase nucleophiles, as revealed by thermogravimetry. Intense luminescence emission is restored for 1b/Nu, Nu = MeCN (1a), acetone, tetrahydrothiophene (THT), and Et2S. Films of 1b are produced when CH2Cl2 solutions of 1a are cast onto glass. The films also react with Nu vapor, again producing intense emission. The pyrazine-bridged dimer [Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2a) is produced in CH2Cl2, while [Cu2(PPh3)4(MeCN)(acetone)(Pyz)](BF4)2∙½[Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2b) is formed in acetone. The crystal structure of the polymer \{[Cu(PPh3)2(Bpy)](BF4)∙acetone\}n (3) is reported, as is the mixed polymer/dimer structure \{[Cu(PPh3)2(Pyz)](BF4)\}n∙½n[Cu2(PPh3)4(BF4)2(Pyz)] (4b) in which the dimer units show Cu–FBF3 coordination. The Pyz dimer and the Pyz and Bpy polymers show much weaker luminescence behavior than that of Bpy dimers 1a and the related 1b/Nu adducts. Nucleophile adduct structures [Cu2(PPh3)4(THT)2(Bpy)](BF4)2∙½ethyl ether (5) and [Cu2(PPh3)4(Py)2(Bpy)](BF4)2∙CH2Cl2 (6) confirmed the coordination of one Nu per Cu to 1b.",

keywords = "Copper, Luminescence, Metal complex film, Metal–organic dimer, Metal–organic polymer, Nucleophile, X-ray crystal structure",

author = "Royzman, \{Dmitry E.\} and Noviello, \{Andrew M.\} and Henline, \{Kylie M.\} and Pike, \{Robert D.\} and Killarney, \{James P.\} and Patterson, \{Howard H.\} and Carlos Crawford and Zerihun Assefa",

year = "2014",

month = jan,

day = "1",

doi = "10.1007/s10904-013-9978-7",

language = "English",

volume = "24",

pages = "66--77",

journal = "Journal of Inorganic and Organometallic Polymers and Materials",

issn = "1574-1443",

publisher = "Springer New York [email protected]",

number = "1",

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TY - JOUR

T1 - Structure, Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers

AU - Royzman, Dmitry E.

AU - Noviello, Andrew M.

AU - Henline, Kylie M.

AU - Pike, Robert D.

AU - Killarney, James P.

AU - Patterson, Howard H.

AU - Crawford, Carlos

AU - Assefa, Zerihun

PY - 2014/1/1

Y1 - 2014/1/1

N2 - The dimeric complex of Cu(I) [Cu2(PPh3)4(MeCN)2(Bpy)](BF4)2 (1a, Bpy = 4,4′-dipyridyl) self-assembles in CH2Cl2 or acetone and shows intense photoluminescence (excitation λmax = 356 nm, emission λmax = 486 nm, ϕ = 0.47). The MeCN ligands are readily removed from 1a, producing [Cu2(PPh3)4(Bpy)](BF4)2 (1b) and altering the photophysical behavior (excitation λmax = 336 nm, emission λmax = 568 nm, ϕ = 0.07). The desolvated compound 1b reversibly absorbs many vapor phase nucleophiles, as revealed by thermogravimetry. Intense luminescence emission is restored for 1b/Nu, Nu = MeCN (1a), acetone, tetrahydrothiophene (THT), and Et2S. Films of 1b are produced when CH2Cl2 solutions of 1a are cast onto glass. The films also react with Nu vapor, again producing intense emission. The pyrazine-bridged dimer [Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2a) is produced in CH2Cl2, while [Cu2(PPh3)4(MeCN)(acetone)(Pyz)](BF4)2∙½[Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2b) is formed in acetone. The crystal structure of the polymer {[Cu(PPh3)2(Bpy)](BF4)∙acetone}n (3) is reported, as is the mixed polymer/dimer structure {[Cu(PPh3)2(Pyz)](BF4)}n∙½n[Cu2(PPh3)4(BF4)2(Pyz)] (4b) in which the dimer units show Cu–FBF3 coordination. The Pyz dimer and the Pyz and Bpy polymers show much weaker luminescence behavior than that of Bpy dimers 1a and the related 1b/Nu adducts. Nucleophile adduct structures [Cu2(PPh3)4(THT)2(Bpy)](BF4)2∙½ethyl ether (5) and [Cu2(PPh3)4(Py)2(Bpy)](BF4)2∙CH2Cl2 (6) confirmed the coordination of one Nu per Cu to 1b.

AB - The dimeric complex of Cu(I) [Cu2(PPh3)4(MeCN)2(Bpy)](BF4)2 (1a, Bpy = 4,4′-dipyridyl) self-assembles in CH2Cl2 or acetone and shows intense photoluminescence (excitation λmax = 356 nm, emission λmax = 486 nm, ϕ = 0.47). The MeCN ligands are readily removed from 1a, producing [Cu2(PPh3)4(Bpy)](BF4)2 (1b) and altering the photophysical behavior (excitation λmax = 336 nm, emission λmax = 568 nm, ϕ = 0.07). The desolvated compound 1b reversibly absorbs many vapor phase nucleophiles, as revealed by thermogravimetry. Intense luminescence emission is restored for 1b/Nu, Nu = MeCN (1a), acetone, tetrahydrothiophene (THT), and Et2S. Films of 1b are produced when CH2Cl2 solutions of 1a are cast onto glass. The films also react with Nu vapor, again producing intense emission. The pyrazine-bridged dimer [Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2a) is produced in CH2Cl2, while [Cu2(PPh3)4(MeCN)(acetone)(Pyz)](BF4)2∙½[Cu2(PPh3)4(MeCN)2(Pyz)](BF4)2 (2b) is formed in acetone. The crystal structure of the polymer {[Cu(PPh3)2(Bpy)](BF4)∙acetone}n (3) is reported, as is the mixed polymer/dimer structure {[Cu(PPh3)2(Pyz)](BF4)}n∙½n[Cu2(PPh3)4(BF4)2(Pyz)] (4b) in which the dimer units show Cu–FBF3 coordination. The Pyz dimer and the Pyz and Bpy polymers show much weaker luminescence behavior than that of Bpy dimers 1a and the related 1b/Nu adducts. Nucleophile adduct structures [Cu2(PPh3)4(THT)2(Bpy)](BF4)2∙½ethyl ether (5) and [Cu2(PPh3)4(Py)2(Bpy)](BF4)2∙CH2Cl2 (6) confirmed the coordination of one Nu per Cu to 1b.

KW - Copper

KW - Luminescence

KW - Metal complex film

KW - Metal–organic dimer

KW - Metal–organic polymer

KW - Nucleophile

KW - X-ray crystal structure

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U2 - 10.1007/s10904-013-9978-7

DO - 10.1007/s10904-013-9978-7

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SN - 1574-1443

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JF - Journal of Inorganic and Organometallic Polymers and Materials

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Structure, Luminescence, and Vapochromism of Bridged Cationic Copper(I) Dimers and Polymers

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