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Oligomers and Polymers of Copper(I) With Dicyanobenzene and Cyanopyridine Ligands
Broderick, Mark K.
Broderick, Mark K.
Abstract
The copper(I) source material Cu(NCMe)4BF4 was reacted with two equivalents of triphenylphosphine and various cyanoaromatic bridging ligands in a variety of solvents to form six new metal-organic complexes. The bridging ligands used were 1,2-dicyanobenzene (oDCB), 1,3-dicyanobenzene (mDCB), 1,4-dicyanobenzene (pDCB), 2-cyanopyridine (oCPy), 3-cyanopyridine (mCPy), and 4-cyanopyridine (pCPy). The resulting complexes consisted of the dimers [Cu2(PPh3)4(oDCB)2](BF4)2 and [Cu2(PPh3)4(oCPy)2](BF4)2, the trimer [Cu3(PPh3)6(mCPy)3](BF4)3, and the polymers {[Cu(PPh3)2(mDCB)](BF4)}∞, {[Cu(PPh3)2(pDCB)](BF4)}∞, and {[Cu(PPh3)2(pCPy)](BF4)}∞. The complexes displayed varying levels of solvent retention during crystallization, leading to complexes of {[Cu(PPh3)2(pCPy)](BF4)}∞ with ½ acetone, [Cu2(PPh3)4(oCPy)2](BF4)2 with two molecules of toluene, {[Cu(PPh3)2(pDCB)](BF4)}∞ with one molecule of dichloromethane, and [Cu2(PPh3)4(oDCB)2](BF4)2 with one molecule of dichloromethane, one-half molecule of dichloromethane, two molecules of chloroform/one molecule of water, or two molecules of tetrahydrofuran. Photophysical analysis of the complexes showed excitation in the 340–400 nm range and emission in the 450–560 nm range for all complexes.
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2016-04-01
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Chemistry