Luminescent Mechanochromism in a Gold(I)鈥揅opper(I) N-Heterocyclic Carbene Complex

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• 作者：Kelly Chen ; Michelle M. Nenzel ; Thomas M. Brown ; Vincent J. Catalano
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：6900-6909
• 全文大小：531K
• ISSN：1520-510X

文摘

The silver(I) species [Ag(benzim(CHb>2b>py)b>2b>)b>2b>]PFb>6b> (<b>1b>) was prepared by refluxing the ligand precursor [H(benzim(CHb>2b>py)b>2b>)b>2b>]PFb>6b> with Agb>2b>O and aqueous sodium hydroxide in dichloromethane. Simple transmetalation of <b>1b> with tetrahydrothiophenegold(I) chloride forms the gold(I) analogue [Au(benzim(CHb>2b>py)b>2b>)b>2b>]PFb>6b> (<b>2b>). The addition of 2 equiv of [Cu(NCCHb>3b>)b>4b>]PFb>6b> to <b>2b> in acetonitrile produces a blue-luminescent, trimetallic complex, [AuCub>2b>(benzim(CHb>2b>py)b>2b>)b>2b>(NCCHb>3b>)b>4b>](PFb>6b>)b>3b>路2CHb>3b>CN (<b>3b>路2CHb>3b>CN). When blue-luminescent <b>3b>路2CHb>3b>CN is exposed to air, the complex loses four acetonitrile molecules, and the emission of the desolvated complex (<b>4b>) appears aquamarine. Crystallization of <b>4b> from different solvents produces the complexes [AuCub>2b>(benzim(CHb>2b>py)b>2b>)b>2b>](PFb>6b>)b>3b> (<b>5b>) and [AuCub>2b>(benzim(CHb>2b>py)b>2b>)b>2b>(NCCHb>2b>CHb>3b>)b>2b>](PFb>6b>)b>3b> (<b>6b>). Upon grinding, both <b>3b>路2CHb>3b>CN and <b>4b> exhibit mechanochromic transformations to a yellow-luminescent powder (ground-<b>4b>). The reversible mechanochromic transformation of <b>3b>路2CHb>3b>CN to ground-<b>4b> is a crystalline-to-amorphous conversion accompanied by partial desolvation. The luminescent mechanochromism of <b>4b> to ground-<b>4b> is an 鈥渁morphous-to-amorphous鈥?process and does not require solvent loss. In addition to their mechanochromic properties, both <b>3b>路2CHb>3b>CN and <b>4b> exhibit luminescent thermochromism through desolvation to form a weak luminescent powder (<b>7b>).