Different Effects of a Cotemplate and [(Transition-Metal)(1,10-Phenanthroline)_m]²⁺ (m = 1–3) Complex Cations on the Self-assembly of a Series of Hybrid Selenidostannates Showing Combined Optical Properties of Organic and Inorganic Components

Abstract

1,10-Phenanthroline (phen) and monoprotonated methylamine molecules were used as a novel cotemplate to direct the formation of a new inorganic-organic hybrid selenidostannate, (CH(3)NH(3))(4)(Sn(2)Se(6))·6phen (1); while the utilization of three types of transition-metal (TM) phen complex cations with the TM/phen ration of 1:1, 1:2, and 1:3 as structure directors affords {[Mn(phen)(2)](2)(μ(2)-Sn(2)Se(6))}·H(2)O (2a), {[Fe(phen)(2)](2)(μ(2)-Sn(2)Se(6))} (2b), {[Mn(phen)](2)(μ(4)-Sn(2)Se(6))}(n) (3), {[Mn(phen)(2)](Sn(2)Se(5))}(n) (4), and [Fe(phen)(3)](n)(Sn(3)Se(7))(n)·1.25nH(2)O (5). These compounds show diverse structures with the selenidostannate anions varying from discrete, μ(2)- and μ(4)- (Sn(2)Se(6))(4-) anions, to one-dimensional (1-D) (1)(∞)(Sn(2)Se(5)(2-)) anionic chains, and two-dimensional (2-D) extended (2)(∞)(Sn(3)Se(7)(2-)) anionic layers, demonstrating different structure-directing abilities of the cotemplate and the three types of TM phen complex cations. This work clearly indicates that the approach of modifying the number of the free coordination sites of unsaturated TM phen complex cations is very exciting as a way to synthesize novel hybrid chalcogenidometalates. Of particular interest, the present compounds exhibit interesting optical properties that reflect the combined effects of both photoluminescence-active organic components and semiconducting inorganic chalcogenidometalate anionic networks.

Haloplumbate hybrids with organically coordinated halometal complexes as templates and mixed halo atoms: Solvothermal syntheses, crystal structures, and optical properties

“…5). These emission bands are similar to that of the phen molecule [12], suggesting that the phen coordinated halometal complexes greatly contributes to the PL of 1-3. Compounds 1-3 show similar emission spectra, but their luminescence intensities gradually decrease from 1 to 3.…”

“…Previous studies have shown that haloplumbate hybrids, with a wide range of interesting optical, semiconducting, and other physical properties, are technically important [7][8][9], and their haloplumbate anions exhibit a wide variety of coordination numbers and stereochemistries due to the flexibility of the Pb(II) coordination polyhedron and the templating effect of the cations [10]. Recent development has revealed that introduction of transition metal (TM) complex cations into inorganic systems can produce inorganicorganic hybrids with unique topological structures and interesting physical properties [11,12]. For example, Mercier and co-workers have synthesized an organic-inorganic hybrid [Cu(O 2 C(CH 2 ) 3 NH 3 ) 2 ] PbBr 4 with copper paddle-wheel clusters linking perovskite layers [13].…”

Transition Metal Complexes with Linkage to the Thiostannate Units Forced by Suitable Amine Molecules

“…The compounds {[Ni(phen) 2 ] 2 [Sn 2 S 6 ]} · biph ( 1 ) and {[Ni(phen) 2 ] 2 [Sn 2 S 6 ]} · phen · H 2 O ( 2 ) consist both of {[Ni(phen) 2 ] 2 [Sn 2 S 6 ]} complexes and additional organic molecules. The structure of {[TM(phen) 2 ] 2 [Sn 2 S 6 ]} is constructed by the linkage of two [Ni(phen) 2 ] 2+ complexes with a bridging [μ‐Sn 2 S 6 ] 4– unit (Figure ), and does not significantly differ from compounds with this motif or compounds containing the analogous selenidostannate and will not be discussed herein in detail. The biphenyl molecule ( 1 ) and the additional phen molecule ( 2 ) are arranged to generate extended π–π interactions with phen ligands of the TM 2+ centered complex.…”

Solvothermal syntheses and characterizations of the first example of lanthanide selenidostannates prepared in mixed ethylene polyamines

“…But in the presence of tetradentate triethylenetetramine (trien) and tris(2-aminoethyl)amine (tren), and pentadentate tetraethylenepentamine (tepa) ligands, or bidentate ligands with higher steric hindrance (such as 1,10-Phenanthroline, phen), unsaturated TM-amine complexes can be formed, and TM-incorporated chalcogenidostannates are obtained. The examples include {[Mn(trien)] 2 SnS 4 }Á4H 2 O [11], [{TM(tren)} 2 (l-Sn 2 S 6 )] (TM = Co, Ni) [12], [{TM(tepa)} 2 (l-Sn 2 S 6 )] (TM = Fe, Co, Ni) [13], [{TM(phen)} 2 (l-Sn 2 Se 6 )] (TM = Mn, Fe) [14], [{Zn(trien)} 2 (l-SnTe 4 )], and [{Zn(tren)} 2 (l-Sn 2 Te 6 )] [15]. The unsaturated coordination site of TM center in TM-amine complexes is completed by the chalcogen atom of the chalcogenidostannate anions in these compounds.…”