Controlling the dimensionality of metal-metal bonded Rrh(2)(4+) polymers by the length of the linker. A disciplined example of crystal engineering.
Reaction of the molecular loop [Rh(2)(cis-DAniF)(2)(CH(3)CN)](2)(malonato)(2), DAniF = N,N'-di-p-anisylformamidinate, with 2 equiv of 2,2',3,3',5,5',6,6'-octafluoro-4,4'-biphenyldinitrile gives a linear tubular structure with Rh-Rh distances of 2.435(1) A. A comparison of the structures obtained with this molecular loop but employing other linkers support the idea that longer linkers favor one-dimensional structures while shorter linkers favor two-dimensional structures because of the increased clashing between the large p-anisyl groups. Crystallographic data at 213(2) K for [[Rh(2)(cis-DAniF)(2)](2)(O(2)CCH(2)CO(2))(2)(NCC(6)F(4)C(6)F(4)CN)(2)] x 6.8nCH(2)Cl(2) are: monoclinic, P2(1)/m, a = 11.802(1), b = 28.303(2), c = 18.820(2) A, beta = 95.673(2) degrees, and Z = 2.
Cotton
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Department of Chemistry and Laboratory for Molecular Structure and Bonding, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA.
Lin
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Murillo
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