Issue 22, 2019

Toward a dodecanuclear molecular Re(i) box: structural and spectroscopic properties

Abstract

Two tetrapyridyl ligands of 1,2,4,5-tetraethynyl(4-pyridyl)benzene (tpeb) and tetra(4-pyridyl)-tetrathiafulvalene (TTF(py)4) were used to react with trinuclear (Re(CO)4)3(C3N3S3) (C3N3S3 = cyanurate trianion) moieties to afford hexanuclear [(Re(CO)3)6(tpeb)2(C3N3S3)2]·4CH3CN·toluene (1) and dodecanuclear [(Re(CO)3)12(TTF(py)4)3(C3N3S3)4]·8CH3CN·12DMF (2) boxes, respectively, under solvothermal conditions. Surprisingly, similar tetrapyridyl ligands with different core units (i.e., benzene and tetrathiafulvalene moieties) led to dramatically different structural motifs (i.e., hexanuclear and dodecanuclear boxes). Complex 1 forms a slightly bent trigonal-prismatic structure, containing two μ3-tpeb ligands and two Re3C3N3S3 moieties as well as a π⋯π interaction distance of 3.86 Å. It is noted that complex 2 features a novel four-star structure, and three crossed tetrathiafulvalene moieties from three μ4-TTF(py)4 ligands to form a triple-decker arrangement with a π⋯π interaction distance of 3.70 Å. Moreover, 1 and 2 display luminescence properties in the solid state along with electrochemical properties for complex 2 arising from the electroactive TTF core.

Graphical abstract: Toward a dodecanuclear molecular Re(i) box: structural and spectroscopic properties

Supplementary files

Article information

Article type
Paper
Submitted
14 Mar 2019
Accepted
09 May 2019
First published
10 May 2019

Dalton Trans., 2019,48, 7946-7952

Toward a dodecanuclear molecular Re(I) box: structural and spectroscopic properties

B. Tzeng, Y. Hsiao, G. Lee, H. Wang, C. F. Leong, D. M. D'Alessandro and J. Zuo, Dalton Trans., 2019, 48, 7946 DOI: 10.1039/C9DT01115C

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