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Single‐Crystal‐to‐Single‐Crystal Transformation and Solvochromic Luminescence of a Dinuclear Gold(I)–(Aza‐[18]crown‐6)dithiocarbamate Compound
Author(s) -
Tzeng BiingChiau,
Chao An
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405466
Subject(s) - intermolecular force , chemistry , dithiocarbamate , luminescence , single crystal , crystallography , xylene , crystal (programming language) , crystal structure , benzene , molecule , materials science , organic chemistry , optoelectronics , computer science , programming language
The treatment of [AuCl(SMe 2 )] with an equimolar amount of NaO 5 NCS 2 (O 5 NCS 2 =(aza‐[18]crown‐6)dithiocarbamate) in CH 3 CN gave [Au 2 (O 5 NCS 2 ) 2 ] ⋅ 2 CH 3 CN ( 2⋅ 2 CH 3 CN), and its crystal structure displays a dinuclear gold(I)‐azacrown ether ring and an intermolecular gold(I) ⋅⋅⋅ gold(I) contact of 2.8355(3) Å in crystal lattices. It is noted that two other single crystals of 2 ⋅ tert ‐butylbenzene⋅H 2 O and 2⋅ 0.5 m ‐xylene can be successfully obtained from a single‐crystal‐to‐single‐crystal (SCSC) transformation process by immersing single crystals of 2⋅ 2 CH 3 CN in the respective solvents, and both also show intermolecular gold(I) ⋅⋅⋅ gold(I) contacts of 2.9420(5) and 2.890(2)–2.902(2) Å, respectively. Significantly, the emissions of all three 2 ⋅solvates are well correlated with their respective intermolecular gold(I) ⋅⋅⋅ gold(I) contacts, where such contacts increase with 2⋅ 2 CH 3 CN (2.8355(3) Å)< 2⋅ 0.5 m ‐xylene (2.890(2)–2.902(2) Å)< 2⋅ tert ‐butylbenzene⋅H 2 O (2.9420(5) Å), and their emission energies increase with 2⋅ 2 CH 3 CN (602 nm)< 2⋅ 0.5 m ‐xylene (583 nm)< 2⋅ tert ‐butylbenzene⋅H 2 O (546 nm) as well. In this regard, we further examine the solvochromic luminescence for some other aromatics, and finally their emissions are within 546–602 nm. Obviously, the above results are mostly ascribed to the occurrence of intermolecular gold(I) ⋅⋅⋅ gold(I) contacts in 2 ⋅solvates, which are induced by the presence of various solvates in the solid state, as a key role to be responsible for their solvochromic luminescence.