TY - JOUR
T1 - Combination chemistry of hexa-copper-substituted polyoxometalates driven by the CuII-polyhedra distortion
T2 - From tetramer, 1D chain to 3D framework
AU - Li, Bing
AU - Zhao, Jun Wei
AU - Zheng, Shou Tian
AU - Yang, Guo Yu
PY - 2009/9/7
Y1 - 2009/9/7
N2 - Reaction of CuCl2 -2H2O and trivacant Keggin polyoxoanion Na9[A-α-PW9O34]-7H 2O in the presence of ethylenediamine/1,2-diaminopropane (en/enMe) under hydrothermal conditions led to five novel inorganic-organic hybrid polyoxotungstates (POTs):[Cu(en)2]2[Cu(en) 2(H2O)]2[Cu(H2O)2] [Cu4(H2O)2(B-a-PW9O 34)2] • 2H2O(1), [Cu6(μ 3OH)3(en)3(H2O)5(B- α-PW9O34)] • 6H2O (2), Na 6{[Cu6(μ3-OH)3(en) 3(H2O)2(B-a-PW9O34)] 2[Cu4(H2O)2(B-a-PW9O 34)2]}.2 H2en-8H2O (3), [Cu 6μ3-OH)3(en)3(H 2O)3(B-αPW9O34)]-4H 2O (4), [CuII6CuI 4(μ6-O)(OH)18] [Cu6(μ3OH)3(enMe)3(H 2O)3(B-α-PW9O34)] 4-4H3O-2H2O (5). 1 is a new 1D chain constructed from alternate tetra-CuII sandwiched units [Cu 4(H2O)2(B-α-PW9O 34)2]10- and dinuclear [CuII 2(H2O)6]4+ units. 2-5 are a series of novel transition-metal substituted polyoxometalates (TMSPs) comprising hexa-CuII substituted (Cu6PW9) units (Cu 6=Cu6(U3OH)3, PW9=B- α-PW9O34, Scheme 1). 2 is an unusual monomer. 3 is an unprecedented tetramer built by two types of TMSP units, [Cu 6PW9(Sn)3(H2O)2] and [CuII4(H2O)2(PW9) 2]10-. 4 is a novel chain assembled from [Cu 6PW9(en)3(H2O)3] units by double-bridging mode. Most interestingly, 5 is a open framework made by [Cu6PW9(enMe)3(H2O)3] units, in which the novel decacopper oxygen clusters, [Cu4Cu II6(μ6-O)(OH)16]4- formed In situ, are encapsulated into the channels, and 5 represents the first decametallic-cluster-containing open framework built by TMSP units. 2-5 all contain the hexa-CuII substituted POT unit {Cu6PW 9L3(H2O)n} (L = en/enMe, n < 6) made by (Cu6L3(H2O)n} core and trivacant Keggin PW9 fragments. Moreover, 3-5 can be viewed as combining derivatives of 2 through substituting water ligands on hexa-Cu II (Cu6L3(H2O)n} units by terminal oxygen atoms of PW9 units. Importantly, the Cu"-polyhedra Jahn-Tell/ pseudo-Jahn-Teller distortion plays a crucial role in the formation of 1-5. The magnetic behaviors of 2-5 show antiferromagnetic interactions between the CuII ions in the hexa-CuII cluster.
AB - Reaction of CuCl2 -2H2O and trivacant Keggin polyoxoanion Na9[A-α-PW9O34]-7H 2O in the presence of ethylenediamine/1,2-diaminopropane (en/enMe) under hydrothermal conditions led to five novel inorganic-organic hybrid polyoxotungstates (POTs):[Cu(en)2]2[Cu(en) 2(H2O)]2[Cu(H2O)2] [Cu4(H2O)2(B-a-PW9O 34)2] • 2H2O(1), [Cu6(μ 3OH)3(en)3(H2O)5(B- α-PW9O34)] • 6H2O (2), Na 6{[Cu6(μ3-OH)3(en) 3(H2O)2(B-a-PW9O34)] 2[Cu4(H2O)2(B-a-PW9O 34)2]}.2 H2en-8H2O (3), [Cu 6μ3-OH)3(en)3(H 2O)3(B-αPW9O34)]-4H 2O (4), [CuII6CuI 4(μ6-O)(OH)18] [Cu6(μ3OH)3(enMe)3(H 2O)3(B-α-PW9O34)] 4-4H3O-2H2O (5). 1 is a new 1D chain constructed from alternate tetra-CuII sandwiched units [Cu 4(H2O)2(B-α-PW9O 34)2]10- and dinuclear [CuII 2(H2O)6]4+ units. 2-5 are a series of novel transition-metal substituted polyoxometalates (TMSPs) comprising hexa-CuII substituted (Cu6PW9) units (Cu 6=Cu6(U3OH)3, PW9=B- α-PW9O34, Scheme 1). 2 is an unusual monomer. 3 is an unprecedented tetramer built by two types of TMSP units, [Cu 6PW9(Sn)3(H2O)2] and [CuII4(H2O)2(PW9) 2]10-. 4 is a novel chain assembled from [Cu 6PW9(en)3(H2O)3] units by double-bridging mode. Most interestingly, 5 is a open framework made by [Cu6PW9(enMe)3(H2O)3] units, in which the novel decacopper oxygen clusters, [Cu4Cu II6(μ6-O)(OH)16]4- formed In situ, are encapsulated into the channels, and 5 represents the first decametallic-cluster-containing open framework built by TMSP units. 2-5 all contain the hexa-CuII substituted POT unit {Cu6PW 9L3(H2O)n} (L = en/enMe, n < 6) made by (Cu6L3(H2O)n} core and trivacant Keggin PW9 fragments. Moreover, 3-5 can be viewed as combining derivatives of 2 through substituting water ligands on hexa-Cu II (Cu6L3(H2O)n} units by terminal oxygen atoms of PW9 units. Importantly, the Cu"-polyhedra Jahn-Tell/ pseudo-Jahn-Teller distortion plays a crucial role in the formation of 1-5. The magnetic behaviors of 2-5 show antiferromagnetic interactions between the CuII ions in the hexa-CuII cluster.
UR - http://www.scopus.com/inward/record.url?scp=69549090532&partnerID=8YFLogxK
U2 - 10.1021/ic900931r
DO - 10.1021/ic900931r
M3 - Article
AN - SCOPUS:69549090532
SN - 0020-1669
VL - 48
SP - 8294
EP - 8303
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 17
ER -