Luminescent Heteronuclear Au^I₅Ag^I₈ Complexes of {1,2,3-C₆(C₆H₄R-4)₃}^3- (R = H, CH₃, Bu^t) by Cyclotrimerization of Arylacetylides

Abstract

Unusual AuI-AgI heterometallic complexes [Au5Ag8(mu-dppm)4{1,2,3-C6(C6H4R-4)3}(CCC6H4R-4)7]3+ (R = H 1, CH3 2, But 3) were isolated by reactions of polymeric silver arylacetylides (AgCCC6H4R-4)n with binuclear gold component [Au2(mu-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane), in which cyclotrimerization of arylacetylide -CCC6H4R-4 affords trianion {1,2,3-C6(C6H4R-4)3}3- with an unprecedented mu5-bonding mode. Compounds 1(SbF6)3-3(SbF6)3 exhibit intense photoluminescence derived from an MLCT (Au5Ag8 --> CCC6H4R-4) transition, mixed with a metal cluster-centered excited states.

A Dinuclear Gold(I)–Silver(I) Derivative of 2‐Cyclopentylidene‐2‐sulfanylacetic Acid and Related Complexes: Synthesis, Crystal Structures, Properties and Antitumor Activity

“…To the best of our knowledge, isolated dinuclear units containing an S-supported Ag-Au interaction have not previously been reported in the literature. [21] Shorter distances were also found in the trinuclear complex [AuAg 2 {(pyCH 2 ) 2 im} 2 (NCCH 3 ) 2 ](BF 4 ) 3 [(pyCH 2 ) 2 im = 1,3-bis(2-pyridylmethyl)imidazole], [22] in the tetranuclear cation [{(Ph 3 P)Au(μ-mes)Ag(thz)} 2 ] 2+ , [23] in the clusters [Au 6 Ag{μ-C 6 H 2 (CHMe 2 ) 3 } 6 ] + , [24] [Au 3 Ag(μ 3 -O)-(PPh 2 py) 3 ] 2+ , [25] [Au 5 Ag 8 (μ-dppm) 4 {1,2,3-C 6 (C 6 H 5 ) 3 }-(CϵCC 6 H 5 ) 7 ] 3+ [26] and (Bu 4 N) 2 [Au(3,5-C 6 F 3 Cl 2 ) 2 Ag 4 -(CF 3 COO) 5 ], [27,28] and in polymers such as [{Au(μ-mes)-AsPh 3 } 2 Ag](ClO 4 ), [29] [AgAu(mtp) 2 ] (mtp = diphenylmethylenethiophosphinato), [30] {[AuAg(Meimpy) 2 (L)](BF 4 ) 2 } n , {[AuAg(Meimpy) 2 (NO 3 )]NO 3 } n (Meimpy = methylimidazolepyridine; L = CH 3 CN, C 6 H 5 CN, C 6 H 5 CH 2 CN), [31] [Au 2 Ag 2 (C 6 F 5 ) 4 (OCMe 2 ) 2 ] n , [32] [Au 2 Ag 2 (C 6 F 5 ) 4 (NC-CH 3 ) 2 ] n , [33] or Ag([Au(μ-C 2 ,N 3 -bzim)] 3 ) 2 ·BF 4 ·CH 2 Cl 2 , [34,35] [AuAg 4 (mes)(CF 3 CO 2 ) 4 (tht)] n , [AuAg 4 (mes)(CF 3 CF 2 -CO 2 ) 4 (tht)] n , [AuAg 4 (mes)(CF 3 CF 2 CO 2 ) 4 (tht) 3 ] n , {[AuAg 4 -(mes)(CF 3 CO 2 ) 4 (tht)(H 2 O)]·H 2 O·CH 2 Cl 2 } n , [17] [AuAg 3 -(C 6 F 5 )(CF 3 CO 2 ) 3 (CH 2 PPh 3 )] n , [36] [AgAu(C 6 F 5 )(CF 3 CO 2 )-(tht)] n , [Ag 2 Au(C 6 Cl 2 F 3 )(CF 3 CO 2 ) 2 (tht)] n , and [AgAu-(C 6 Cl 5 )(CF 3 CO 2 )(tht)] n . [21] Shorter distances were also found in the trinuclear complex [AuAg 2 {(pyCH 2 ) 2 im} 2 (NCCH 3 ) 2 ](BF 4 ) 3 [(pyCH 2 ) 2 im = 1,3-bis(2-pyridylmethyl)imidazole], [22] in the tetranuclear cation [{(Ph 3 P)Au(μ-mes)Ag(thz)} 2 ] 2+ , [23] in the clusters [Au 6 Ag{μ-C 6 H 2 (CHMe 2 ) 3 } 6 ] + , [24] [Au 3 Ag(μ 3 -O)-(PPh 2 py) 3 ] 2+ , [25] [Au 5 Ag 8 (μ-dppm) 4 {1,2,3-C 6 (C 6 H 5 ) 3 }-(CϵCC 6 H 5 ) 7 ] 3+ [26] and (Bu 4 N) 2 [Au(3,5-C 6 F 3 Cl 2 ) 2 Ag 4 -(CF 3 COO) 5 ], [27,28] and in polymers such as [{Au(μ-mes)-AsPh 3 } 2 Ag](ClO 4 ), [29] [AgAu(mtp) 2 ] (mtp = diphenylmethy...…”

Self‐Assembly of Supramolecular Luminescent AuI–CuI Complexes: “Wrapping” an Au6Cu6 Cluster in a [Au3(diphosphine)3]3+ “Belt”

“…Optimization of the reaction conditions (Scheme 1) allowed selective preparation of [Au 3 (PPh 2 (C 6 H 4 ) 2 PPh 2 ) 3 -{Au 6 Cu 6 (C 2 Ph) 12 }](PF 6 ) 3 (3). The composition of 3 was established on the basis of its 1 H, 13 C, and 31 P NMR and ESI-MS data.…”

A Luminescent Heteronuclear Cluster Featuring an Unusual Cu6 Boat‐Shaped Core Assembled by Two Dialkynyl‐Cycloplatinated Units

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] Compared with polynuclear homometallic alkynyl complexes, the design of heterometallic complexes and/or multicomponent arrays has received less attention. [1,7,8,10,12,[14][15][16][17][18][19][20][21] In this area, considerable interest has been paid to Pt II -M I (M = Cu, Ag, Au) heterometallic alkynyl complexes due to their rich structural topology [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] and interesting spectroscopic and optical properties. [1,14,…”