Abstrakti
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.
Alkuperäiskieli | Englanti |
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Sivut | 480-489 |
Sivumäärä | 10 |
Julkaisu | ORGANOMETALLICS |
Vuosikerta | 36 |
Numero | 2 |
DOI - pysyväislinkit | |
Tila | Julkaistu - 23 tammik. 2017 |
OKM-julkaisutyyppi | A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä |
Sormenjälki
Sukella tutkimusaiheisiin 'Silver Alkynyl-Phosphine Clusters: An Electronic Effect of the Alkynes Defines Structural Diversity'. Ne muodostavat yhdessä ainutlaatuisen sormenjäljen.Tietoaineistot
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CCDC 1537888: Experimental Crystal Structure Determination
Chen, Y. (Contributor), Chou, P.-T. (Contributor), Grachova, E. V. (Contributor), Karttunen, A. (Creator), Koshevoy, I. O. (Contributor), Krytchankou, I. S. (Contributor) & Tunik, S. P. (Contributor), Cambridge Crystallographic Data Centre , 1 tammik. 2017
DOI - pysyväislinkki: 10.5517/ccdc.csd.cc1nm99w, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nm99w&sid=DataCite
Tietoaineisto: Dataset
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CCDC 1537890: Experimental Crystal Structure Determination
Chen, Y. (Contributor), Chou, P.-T. (Contributor), Grachova, E. V. (Contributor), Karttunen, A. (Creator), Koshevoy, I. O. (Contributor), Krytchankou, I. S. (Contributor) & Tunik, S. P. (Contributor), Cambridge Crystallographic Data Centre , 1 tammik. 2017
DOI - pysyväislinkki: 10.5517/ccdc.csd.cc1nm9cy, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nm9cy&sid=DataCite
Tietoaineisto: Dataset
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CCDC 1537886: Experimental Crystal Structure Determination
Chen, Y.-T. (Creator), Krytchankou, I. S. (Creator), Karttunen, A. (Creator), Grachova, E. V. (Creator), Tunik, S. P. (Creator), Chou, P.-T. (Creator) & Koshevoy, I. O. (Creator), Cambridge Crystallographic Data Centre , 14 maalisk. 2017
DOI - pysyväislinkki: 10.5517/ccdc.csd.cc1nm97t, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1nm97t&sid=DataCite
Tietoaineisto: Dataset
Laitteet
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Raaka-aineiden tutkimusinfrastruktuuri
Karppinen, M. (Manager)
Kemian tekniikan korkeakouluLaitteistot/tilat: Facility