TY - JOUR

T1 - Silver Alkynyl-Phosphine Clusters

T2 - An Electronic Effect of the Alkynes Defines Structural Diversity

AU - Chen, Yi Ting

AU - Krytchankou, Ilya S.

AU - Karttunen, Antti J.

AU - Grachova, Elena V.

AU - Tunik, Sergey P.

AU - Chou, Pi Tai

AU - Koshevoy, Igor O.

N1 - Funding Information: Financial support from the Academy of Finland (grant 268993, I.O.K.) and the Ministry of Science and Technology in Taiwan are gratefully acknowledged. Computational resources were provided by CSC, the Finnish IT Center for Science (A.J.K.). Publisher Copyright: © 2017 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2017/1/23

Y1 - 2017/1/23

N2 - The face-capping triphosphine, 1,1,1-tris(diphenylphosphino)methane (tppm), together with bridging alkynyl ligands and the counterions, facilitates the formation of a family of silver complexes, which adopt cluster frameworks of variable nuclearity. The hexanuclear compounds [Ag6(C2C6H4-4-X)3(tppm)2(An-)3] (X = H (1), CF3 (2), OMe (3), An- = CF3SO3- X = OMe (4), An- = CF3COO-) are produced for the electron-accepting to moderately electron-donating alkynes and the appropriate stoichiometry of the reagents. 1 and 3 undergo an expansion of the metal core when treated with 1 equiv of Ag+ to give the species [Ag7(C2C6H4-4-X)3(tppm)2(CF3SO3)3](CF3SO3) (X = H (5), OMe (6)). The electron-donating substituent (X = NMe2) particularly favors this Ag7 arrangement (7) that undergoes geometry changes upon alkynylation, resulting in the capped prismatic cluster [Ag7(C2C6H4-4-NMe2)4(tppm)2(CF3SO3)](CF3SO3)2 (8). Alternatively, for the aliphatic tBu-alkyne, only the octanuclear complex [Ag8(C2But)4{(PPh2)3CH}2(CF3SO3)2](CF3SO3)2 (9) is observed. The structures of 1-4 and 6-9 were determined by X-ray diffraction analysis. In solution, all the studied compounds were found to be stereochemically nonrigid that prevented their investigation in the fluid medium. In the solid state, clusters 2, 3, 5-8 exhibit room temperature luminescence of triplet origin (maximum φem = 27%, λem = 485-725 nm). The observed emission is assigned mainly to [d(Ag) → π∗(alkyne)] electronic transitions on the basis of TD-DFT computational analysis.

AB - The face-capping triphosphine, 1,1,1-tris(diphenylphosphino)methane (tppm), together with bridging alkynyl ligands and the counterions, facilitates the formation of a family of silver complexes, which adopt cluster frameworks of variable nuclearity. The hexanuclear compounds [Ag6(C2C6H4-4-X)3(tppm)2(An-)3] (X = H (1), CF3 (2), OMe (3), An- = CF3SO3- X = OMe (4), An- = CF3COO-) are produced for the electron-accepting to moderately electron-donating alkynes and the appropriate stoichiometry of the reagents. 1 and 3 undergo an expansion of the metal core when treated with 1 equiv of Ag+ to give the species [Ag7(C2C6H4-4-X)3(tppm)2(CF3SO3)3](CF3SO3) (X = H (5), OMe (6)). The electron-donating substituent (X = NMe2) particularly favors this Ag7 arrangement (7) that undergoes geometry changes upon alkynylation, resulting in the capped prismatic cluster [Ag7(C2C6H4-4-NMe2)4(tppm)2(CF3SO3)](CF3SO3)2 (8). Alternatively, for the aliphatic tBu-alkyne, only the octanuclear complex [Ag8(C2But)4{(PPh2)3CH}2(CF3SO3)2](CF3SO3)2 (9) is observed. The structures of 1-4 and 6-9 were determined by X-ray diffraction analysis. In solution, all the studied compounds were found to be stereochemically nonrigid that prevented their investigation in the fluid medium. In the solid state, clusters 2, 3, 5-8 exhibit room temperature luminescence of triplet origin (maximum φem = 27%, λem = 485-725 nm). The observed emission is assigned mainly to [d(Ag) → π∗(alkyne)] electronic transitions on the basis of TD-DFT computational analysis.

UR - http://www.scopus.com/inward/record.url?scp=85018508263&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.6b00866

DO - 10.1021/acs.organomet.6b00866

M3 - Article

VL - 36

SP - 480

EP - 489

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 2

ER -