Gaining an understanding of the growth mechanism from single atoms to clusters and bulk materials continues to present a challenge.Thus,it is important to explore the evolving trends of clusters in the structure and p...Gaining an understanding of the growth mechanism from single atoms to clusters and bulk materials continues to present a challenge.Thus,it is important to explore the evolving trends of clusters in the structure and properties during the size evolution.In this work,we report the synthesis and characterization of two medium-sized chain-like polyarsenic anions.[As_(21)]^(3-)represents a trimeric example of polyarsenic anion assembled through oxidative coupling of As_(7)^(3-)anions.The anion As_(18)^(4-)included in[As_(18)MO_(2)(CO)_(8)]^(4-)is regarded as formed by two realgar-type As_(8)subunits connected by a dinuclear AsAs dumbbell.The As_(18)cluster was previously predicted by theory,and this is the first time successfully synthesized using wet chemistry method.Besides,small-sized polyarsenides As_(2)^(2-)and As_(10)^(2-)were found in compound[K(18-crown-6)]_(3)[As_(10)]_(0.5)[As_(4){Mo(CO)_(3)}_(2)]_(0.5)·2en.Among these,the former exhibits coordination with metal atoms.Single-crystal X-ray diffraction combined with quantum chemical calculations revealed the formation of double bonded As_(2)^(2-)stabilized by metal carbonyl groups.This work demonstrates a novel synthetic approach for the preparation of new polyarsenides and highlights their intriguing bonding characteristics,laying the foundation for the synthesis of such compounds and paving the way for their potential applications.展开更多
Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible in...Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible intermediate,cluster 1,was isolated from the solution phase through subtle changes in reaction conditions in the formation process of complex 2.Hence,we establish the pathway of the bimetallic bridged clusters[Cu_(2)As_(14)]^(4-)by the oxidation of the[As_(7)Cu(PPh_(3))]^(2-).Quantum chemical calculations reveal the presence of metallophilic interaction in clusters 2 and 3.展开更多
基金supported by the National Natural Science Foundation of China(Nos.92161102,21971118 to Z.-M.Sun)the Natural Science Foundation of Tianjin City(Nos.20JCYBJC01560 and 21JCZXJC00140 to Z.-M.Sun)+1 种基金the Fundamental Research Program of Shanxi Province(No.202203021222248)the Taiyuan Normal University College Students Science and Technology Innovation Project(No.CXCY2278)。
文摘Gaining an understanding of the growth mechanism from single atoms to clusters and bulk materials continues to present a challenge.Thus,it is important to explore the evolving trends of clusters in the structure and properties during the size evolution.In this work,we report the synthesis and characterization of two medium-sized chain-like polyarsenic anions.[As_(21)]^(3-)represents a trimeric example of polyarsenic anion assembled through oxidative coupling of As_(7)^(3-)anions.The anion As_(18)^(4-)included in[As_(18)MO_(2)(CO)_(8)]^(4-)is regarded as formed by two realgar-type As_(8)subunits connected by a dinuclear AsAs dumbbell.The As_(18)cluster was previously predicted by theory,and this is the first time successfully synthesized using wet chemistry method.Besides,small-sized polyarsenides As_(2)^(2-)and As_(10)^(2-)were found in compound[K(18-crown-6)]_(3)[As_(10)]_(0.5)[As_(4){Mo(CO)_(3)}_(2)]_(0.5)·2en.Among these,the former exhibits coordination with metal atoms.Single-crystal X-ray diffraction combined with quantum chemical calculations revealed the formation of double bonded As_(2)^(2-)stabilized by metal carbonyl groups.This work demonstrates a novel synthetic approach for the preparation of new polyarsenides and highlights their intriguing bonding characteristics,laying the foundation for the synthesis of such compounds and paving the way for their potential applications.
基金supported by the National Natural Science Foundation of China(21971118 to Z.-M.S.).
文摘Polyarsenides containing coinage metals,[As_(7)Cu(PPh_(3))]^(2-)(1)and[M_(2)As_(14)]^(4-)(M=Cu,2;Ag,3),were synthesized by reactions of the nominal composition K_(3)As_(7) with Group 11 metal complexes.The possible intermediate,cluster 1,was isolated from the solution phase through subtle changes in reaction conditions in the formation process of complex 2.Hence,we establish the pathway of the bimetallic bridged clusters[Cu_(2)As_(14)]^(4-)by the oxidation of the[As_(7)Cu(PPh_(3))]^(2-).Quantum chemical calculations reveal the presence of metallophilic interaction in clusters 2 and 3.
