Synthesis and Structure of a Novel Silver(I) Perchlorate 2,2′:6′,2″-Terpyridine Adduct Solvated With Acetonitrile

Abstract

Recrystallization of an equimolar mixture of silver(I) perchlorate and 2,2′:6′,2″-terpyridine ( terpy ) from acetonitrile solution yields the golden yellow crystalline adduct shown by a room-temperature single-crystal X-ray study to be [Ag3( terpy )4][( MeCN )Ag( terpy )](ClO4)4. Crystals are triclinic, Pī , a 21.48(1), b 14.525(7), c 13.506(8) Ǻ, α 68.50(4), β 80.71(4), γ 81.66(4)°, Z 2 formula units; R was 0.045 for 9681 'observed' reflections. The complex helical cation is quasi- centrosymmetric with a collinear Ag3 array. The environment of the central silver atom is planar four-coordinate, two short Ag-N distances [(2.198(5), 2.188(5)Ǻ] arising from the nitrogen atoms of outer rings of a pair of twisted terpy ligands ; the other two sites are occupied by the nitrogen atoms of the central terpy rings which bifurcate to the other silver atoms [Ag(central)-N(central) 2.624(5), 2.818(5)Ǻ; Ag(outer)-N(central) 2.704(4), 2.640(4)Ǻ], which are also coordinated by the outer ring nitrogen of the two ligands [Ag-N, 2.266(5), 2.304(4) Ǻ]. Coplanar with the latter, each outer silver atom has a further tridentate terpy coordinated [Ag-N(central) 2.362(4), 2.381(4)Ǻ; Ag-N(outer) 2.403(6)-2.573(5)Ǻ]. The [( MeCN )Ag( terpy )]+ species is also quasi-planar, Ag- NCMe being 2.174(7)Ǻ, opposed to the central ring nitrogen [2.331(5)Ǻ; Ag-N(outer) being 2.399(7), 2.433(7)Ǻ].

Economical Design in Noncovalent Nanoscale Synthesis: Diverse Photofunctional Nanostructures Based on a Single Covalent Building Block

“…Pd, Pt, and Ag metal centers were chosen to modify the assemblies as the reaction of terpy with these metals gives square planar complexes 14. The similar geometries of the complexes should allow a better insight into metal‐dependent modification of nanoscale systems.…”

Structural Studies, Antimicrobial Activity and Protein Interaction of Photostable Terpyridine Silver(I) Complexes

“…Solution 1 H and [ 1 H– 15 N] heteronuclear multiple bond coherence (HMBC) NMR spectra of ligands (L PY and L morph ) and complexes ( 1 , 2 ) were recorded in the following solvents; CD 3 SOCD 3 , CD 3 CN, and CD 3 OD to distinguish the different coordination environment around silver(I) in the solution. In general, recrystallization of Ag(I) terpyridine complexes from CH 3 CN afforded [Ag(tpy)(CH 3 CN)] + , . 1 H NMR spectrum of 1 in CD 3 CN showed eight signals (Figure ).…”

“…Some cut‐off evidences for formation of double‐helical structure, [{Ag(tpy)(CH 3 CN)}] 2 (PF 6 ) 2 , and presence of metal‐metal bond in the weakly coordinating solvents were obtained by Constable group . Self‐organization of silver(I) perchlorate and tpy into [Ag 3 (tpy) 4 ][Ag(tpy)(CH 3 CN)](ClO 4 ) 4 was confirmed by analysis of its crystal structure . A photoluminescent double‐helical [Ag 4 (tpy‐4′‐phen) 4 ](PF 6 ) 4 · (CH 3 COCH 3 ) 4 (tpy‐4′‐phen = 4′‐phenyl‐2,2′:6′,2′′‐terpyridine) was synthesized; while two Ag(I) centres are four‐coordinated, the others are two‐coordinated.…”

“…The coordination geometries of Ag(I) ion include linear, trigonal planar, tetrahedral, and trigonal‐bipyramidal , . The coordination chemistry of 2,2′:6′,2′′‐terpyridine (tpy) towards Ag(I) is a subject of interest encouraged by the exciting photophysical properties . Normally, tpy behaves towards metal ions as a planar tridentate ligand, and in rarely examples tpy acts as a bidentate ligand with a free pyridine arm .…”

A planar silver complex of 2,2′:6′,2″:6″,2‴-quaterpyridine

“…The 2,2 0 :6 0 ,2 00 :6 00 ,2 000 :6 000 ,2 000 0 -quinquepyridine (qpy) derivative [Ag(qpy)][PF 6 ] contains pentacoordinated silver in an almost planar mononuclear cation [7], while with 6,6 000 0 -dimethyl-quinquepyridine(dmqpy) and 6,6 000 0 -dimethyl-4 0 ,4 000 -diphenyl-2,2 0 :6 0 ,2 00 :6 00 ,2 000 :6 000 ,2 000 0 -quinquepyridine (dmpqpy), the dinuclear doublehelical silver(I) complexes [ [10]; the latter also exhibits trinuclear helical [Ag 3 -(tpy) 4 ] 3+ cations, thus suggesting that small energy differences are associated with the assembly modes. Another example of approximately planar coordination was found in [Ag 2 (dptz) 2 ][O 3 SCF 3 ] 2 [11], containing the multinucleating ligand 3,6-bis(2-pyridyl)pyridazine (dptz).…”