Heterobimetallic Coordination Polymers Based on the [Pt(SCN)4]2– and [Pt(SeCN)4]2– Building Blocks

New complexes and the first coordination polymers containing [Pt­(SCN)4]2– of the type [M­(L)x]­[Pt­(SCN)4] (where L = 2,2′-bipyridine (bipy), x = 2, M = Co­(II), Ni­(II), Cu­(II); L = ethylenediamine (en), x = 2, M = Ni­(II), Cu­(II); L = N,N,N′,N′-tetramethylethylenediamine (tmeda), x = 1, M = Cu­(II); L = 2,2′;6′,2″-terpyridine (terpy), x = 1, M = Mn­(II), Co­(II); L = 1,10-phenanthroline (phen), x = 2, M = Pb­(II)) were prepared by reacting the appropriate metal–ligand cations with K2[Pt­(SCN)4] and structurally characterized. [M­(bipy)2Pt­(SCN)4]2·2MeOH (M = Co (1), Cu (4)) consist of supramolecular tetranuclear distorted squares containing two [M­(bipy)2]2+ and two [Pt­(SCN)4]2+ units. [Cu­(bipy)2(NCS)]2[Pt­(SCN)4] (6) is a double salt of the [Pt­(SCN)4]2– anion and two [Cu­(bipy)­(NCS)]+ cations. [Cu­(en)2Pt­(SCN)4] (7, 8) are 1-D coordination polymers that are coordinated in either cis or trans fashion at the [Pt­(SCN)4]2– unit, for 7 and 8, respectively. Complexes [Cu­(en)2Pt­(SeCN)4] (9) and [Ni­(en)2Pt­(SCN)4] (10) are similar to 8 and 7, respectively, but complex 9 (prepared using (nBu4N)2[Pt­(SeCN)4]) also presents intermolecular Se–Se interactions which resulted in an increased dimensionality. Compounds [M­(terpy)­Pt­(SCN)4] (M = Mn (11), Co (13)) involve 2-D sheets of [M­(terpy)]2+ and [Pt­(SCN)4]2– units, whereas [Mn­(terpy)2]­[Pt­(SCN)4] (12) is a double salt of one [Mn­(terpy)2]2+ unit and one [Pt­(SCN)4]2–. [Cu­(tmeda)­Pt­(SCN)4] (14) contains a five-coordinate Cu2+ metal center coordinated to one tmeda ligand and three different [Pt­(SCN)4]2– units, resulting in 2-D sheets. [Pb­(phen)2Pt­(SCN)4] (15) contains an 8-coordinate Pb2+ metal center coordinated to two phen ligands and four [Pt­(SCN)4]2–, generating a 3-D network in the solid state. Structural correlations were established between the ancillary ligand, the choice of metal, the structure of the [Pt­(SCN)4]2– building block, and the resulting dimensionality of the coordination polymers.