H 3 {[ Cu( en) 2 ] 5 [ ( VO) 12 O 6 B 18 O 42 ] }[ B( OH) 3 ] 2 16 H 2 O

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1 , ACTA CHIMICA SINICA Vol 62, 2004 No 4, H 3 {[ Cu( en) 2 ] 5 [ ( VO) 12 O 6 B 18 O 42 ] }[ B( OH) 3 ] 2 16 H 2 O a Ξ, a, b a, b a a a Ξ ( a ) ( b ) H 3 BO 3, NH 4 VO 3, Cu (CH 3 COO) 2 H 2 O H 3 {[ Cu (en) 2 ] 5 2 [ (VO) 12 O 6 B 18 O 42 ]}[B(OH) 3 ] 2 16H 2 O, X -, B 18 O B ( 3 2O) V V 6 O 18, [ (VO) 12 O 6 B 18 O 42 ] 13-4 [ Cu(en) 2 ] 2 +, nm,,, Hydrothermal Synthesis, Crystal Structure and Properties of Polyoxovanadium Borate H 3 { [ Cu( en) 2 ] 5 [ ( VO) 12 O 6 B 18 O 42 ] } [ B( OH) 3 ] 2 16 H 2 O LIN, Zhi2Hua a ZHANG, Han2Hui Ξ, a, b HUANG, Chang2Cang a, b SUN, Rui2Qing a CHEN, Yi2Ping a WU, Xiao2Yuan a ( a Department of Chemistry, Fuzhou University, Fuzhou ) ( b State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou ) Abstract A novel polyoxovanadium borate H 3 {[ Cu (en) 2 ] 5 [ (VO) 12 O 6 B 18 O 42 ]} [ B (OH) 3 ] 2 16H 2 O has been synthesized from a mixture of H 3 BO 3, NH 4 VO 3, Cu ( CH 3 COO) 2 H 2 O and ethylenediamine under hydrothermal condition and characterized by crystal X2ray structure analysis, IR spectrum, Raman spectrum, UV2Vis DRIS spectrum, fluorescence spectrum, ESR and TGA In the structure of the compound, there is a ring of B 18 O 42 sandwiched between two vanadium2oxygen clusters V 6 O 18 by eighteen B ( 3 2O) V bonds, and the anion clusters [ (VO) 12 O 6 B 18 O 42 ] 13 - are connected through four [ Cu ( en) 2 ] 2 + by the static electronic interaction Thus, the complex was extended to an infinite two2dimensional network structure, with size of the hole amounting to nm Keywords hydrothermal synthesis, polyoxovanadium borate, crystal structure, cluster compound,,, [1], [2], Ξ E2mail : edu cn Received April 8, 2003 ; revised and accepted October 13, 2003 (No E ) (No K02028)

2 392 Vol 62, 2004 B V O [3] 1997 (enh) 2 4 ml 016 ml, ph 812 (enh 2 ) 4 [ (VO) 12 B 17 O 38 (OH) 8 ] H 2 O, (enh 2 ) 5 [ (VO) 12 O 6 {B 3 O 6 2 (OH) } 6 ] H 2 O [4] 1999 [ Zn (en) 2 ] 6 [ (VO) 12 O 6 B 18 2 O 39 (OH) 3 ] 13H 2 O [2] [Ni2, B 80 % ( (en) 2 ] 6 [ (VO) 12 O 6 B 18 O 39 (OH) 3 ] 8H 2 O [5], %),C 7184 (7174), N 8198 (9103), H 3176 (3190) B 18 O 39 (OH) 3 9 B ( 3 2O) V 1 3 X V 6 O 18,6 [Ni (en) 2 ] Ni ( mm 0130 mm 0148 mm, Rigaku R2 O) B B 18 O 39 (OH) AXIS Parid Weissenberg IP (293 2) K, 3 [ Cu(en) 2 ] 2 + Mo K ( = nm),, H 3 {[ Cu ( en) 2 ] 5 2, Lp, I > 2 ( I) 9422 [ (VO) 12 O 6 B 18 O 42 ]}[B (OH) 3 ] 2 16H 2 O, X Cu - V,, 1 a = (1) nm, b = (2) nm, c = (2) 1 1 nm, = (4), = (5), = (4), V = H 3 BO 3, NH 4 VO 3, Cu(CH 3 COO) 2 H 2 O ( 5) nm 3, Z = 1, M r = , D c = g/ cm 3, Vario EL III,Perkin2Elmer Spectrum 2000 FTIR F(000) = 1558, = mm - 1, R 1 = , wr 2 =,Nicolet 910 FT2Raman,Perkin2Elmer Lambda 900, Edinburgh2Instrument F920, Perkin2Elmer TGA 7,Rigaku R2AXIS Parid Weissenberg IP J EOL J ES FEXG ESR 815, 20 ml, d, 2554 e nm e nm - 3 :, P21, , S = 11005, ( / ) max = 01000, P [6 SHELXTL297,7] NH 4 VO 3 (01234 g, 2 mmol), H 3 BO 3 (11236 g, 20 mmol) 1, Cu(CH 3 COO) 2 H 2 O (01600 g, 3 mmol), 2 1 ( 10 4 ) ( 10 5 nm 2 ) Table 1 Atomic coordination ( 10 4 ) and thermal parameters ( 10 5 nm 2 ) for the title compound Atom x y z U eq Atom x y z U eq Cu(1) (1) 3753(1) - 888(1) 32 (1) O(2) - 377(3) 3789 (2) 2239(3) 19 (1) Cu(2) (1) O(3) - 867(3) 5372 (2) 2506(3) 25 (1) Cu(3) (1) O(4) (3) 4359 (2) 2794(3) 23 (1) Cu(4) (1) O(5) (3) 2925 (3) 2784(3) 24 (1) V(1) (1) 3921(1) 2081 (1) 20 (1) O(6) (4) 6078 (3) 2210(3) 34 (1) V(2) (1) 5775(1) 3082 (1) 21 (1) O(7) - 205(3) 6991 (3) 3989(3) 24 (1) V(3) - 341(1) 7346(1) 5214 (1) 19 (1) O(8) (3) 6044 (2) 4307(3) 23 (1) V(4) (1) 5497(1) 5386 (1) 19 (1) O(9) - 683(3) 8234 (3) 5167(3) 32 (1) V(5) (1) 3448(1) 5592 (1) 19 (1) O(10) 1366 (3) 8026 (2) 6163(3) 21 (1) V(6) (1) 3276(1) 3326 (1) 21 (1) O(11) - 540(3) 6725 (2) 6259(3) 24 (1) B (1) - 181(5) 7448(4) 1889 (5) 26 (1) O(12) (3) 5690 (3) 5412(3) 31 (1) B (2) 727 (5) 7556(4) 3770 (4) 21 (1) O(13) (3) 4846 (2) 6440(3) 23 (1) B (3) 2143 (4) 8219(4) 5698 (5) 21 (1) O(14) (3) 4096 (2) 4501(3) 22 (1) B (4) 3666 (5) 9375(4) 7491 (5) 30 (1) O(15) (3) 2836 (3) 5734(3) 26 (1) B (5) 1905 (4) 7992(4) 7285 (4) 21 (1) O(16) (3) 3204 (2) 6599(3) 20 (1) B (6) 183 (5) 7075(4) 7427 (5) 22 (1) O(17) (3) 2663 (3) 4401(3) 24 (1)

3 No 4 : H 3 {[ Cu(en) 2 ] 5 [ (VO) 12 O 6 B 18 O 42 ]} 393 Atom x y z U eq Atom x y z U eq B (7) (5) 6637(4) 8216 (5) 25 (1) O(18) (3) 2501 (3) 2534(3) 33 (1) B (8) - 681(5) 5315(4) 7593 (5) 21 (1) O(19) - 549(5) 7900 (3) 1126(4) 45 (1) B (9) - 88(5) 3985(4) 7665 (5) 22 (1) O(20) - 324(3) 6514 (3) 1568(3) 26 (1) B (10) 2903 (11) 115(10) - 95(9) 75 (3) O(21) 321 (3) 7984 (3) 2918(3) 26 (1) C(1) (6) 3188(6) - 401(6) 47 (2) O(22) 1671 (3) 8378 (2) 4698(3) 22 (1) C(2) (7) 2380(6) (6) 56 (2) O(23) 3246 (3) 9134 (3) 6436(3) 26 (1) C(3) (8) 4246(8) - 572(8) 69 (2) O(24) 4762 (4) 10155(4) 8116(4) 62 (2) C(4) (9) 5190(7) - 554(8) 69 (2) O(25) 3047 (3) 8884 (3) 7935(3) 25 (1) C(5) 3826 (5) 378 (5) 3084 (6) 41 (1) O(26) 1242 (3) 7965 (2) 7775(3) 21 (1) C(6) 7068 (5) 172 (5) 6627 (5) 38 (1) O(27) - 422(3) 7323 (3) 7919(3) 25 (1) C(7) (7) 6874(6) 6409 (6) 49 (2) O(28) (4) 6871 (3) 8680(4) 39 (1) C(8) (6) 6103(5) 6950 (6) 47 (2) O(29) (3) 5679 (3) 8073(3) 25 (1) C(9) 2122 (9) 10593(9) 6899 (9) 83 (3) O(30) - 431(3) 4604 (2) 8082(3) 21 (1) C(10) 1561 (11) 11131(9) 7148 (9) 92 (4) O(31) 3723 (7) - 82(7) - 150(5) 97 (3) N(1) (4) 4112(4) - 400(4) 37 (1) O(32) 1756 (7) - 432(7) - 791(7) 110 (3) N(2) (5) 2324(4) (5) 44 (1) O(33) 3301 (7) 959 (7) 743(6) 98 (3) N(3) (5) 3410(5) (5) 48 (1) OW1-3324(4) 3998 (3) (3) 37 (1) N(4) (5) 5194(4) - 339(5) 46 (1) OW (4) (4) 3755(4) 47 (1) N(5) 4949 (4) 883 (4) 4058 (4) 33 (1) OW3-3639(5) 6412 (4) 3300(5) 57 (1) N(6) 6695 (4) 789 (3) 5990 (4) 32 (1) OW4-3314(6) 8019 (4) 4738(5) 67 (2) N(7) (4) 6369(4) 5259 (5) 37 (1) OW5-1513(7) 8479 (6) 6717(6) 80 (2) N(8) (5) 5286(4) 6581 (5) 43 (1) OW (8) 1395 (5) 1215(7) 91 (2) N(9) 1644 (5) 10290(4) 5743 (6) 49 (2) OW7 58 (9) - 48(6) 1365(8) 112 (3) N(10) 324 (6) 10537(5) 6478 (5) 56 (2) OW (4) O(1) (3) 3461(3) 835 (3) 32 (1) OW (14) 1799(12) - 154(11) 125 (8) U eq = (1/ 3) i j U ij a i 3 a j 3 a i a j ; 3 : The occupancy is (nm) ( ) Table 2 Selected bond lengths (nm) and bond angles ( ) Cu(1) N(1) (5) V(2) O(7) (3) B (1) O(21) (7) B (8) O(29) (6) Cu(1) N(2) (5) V(2) V(3) (12) B (1) O(19) (7) B (8) O(2) # (6) Cu(1) N(3) (5) V(3) O(9) (4) B (2) O(22) (6) B (9) O(30) (6) Cu(1) N(4) (6) V(3) O(11) (4) B (2) O(21) (6) B (9) O(20) # (7) Cu(1) OW (4) V(3) O(7) (3) B (2) O(7) (6) B (9) O(3) # (6) Cu(1) O(1) (4) V(3) O(8) (3) B (2) O(16) # (6) B (9) O(16) (7) Cu(2) N(6) (5) V(3) O(10) (3) B (3) O(22) (7) B (10) O(32) (14) Cu(2) N(5) (5) V(3) V(4) (10) B (3) O(23) (6) B (10) O(31) (14) Cu(2) OW (5) V(4) O(12) (3) B (3) O(17) # (6) B (10) O(33) (14) Cu(3) N(7) (5) V(4) O(11) (3) B (3) O(10) (6) C(1) N(1) (9) Cu(3) N(8) (6) V(4) O(8) (3) B (4) O(23) (8) C(1) C(2) (10) Cu(3) O(12) (4) V(4) O(13) (4) B (4) O(25) (7) C(2) N(2) (10) Cu(4) N(9) (6) V(4) O(14) (3) B (4) O(24) (7) C(3) C(4) (15) Cu(4) N(10) (7) V(4) V(5) (11) B (5) O(26) (6) C(3) N(3) (11) Cu(4) O(9) (4) V(5) O(15) (3) B (5) O(25) (6) C(4) N(4) (11) V(1) O(1) (4) V(5) O(13) (3) B (5) O(5) # (6) C(5) N(5) (8) V(1) O(5) (3) V(5) O(17) (3) B (5) O(10) (7) C(5) C(6) # (8) V(1) O(3) (3) V(5) O(14) (3) B (6) O(26) (6) C(6) N(6) (8) V(1) O(2) (3) V(5) O(16) (3) B (6) O(11) (7) C(6) C(5) # (8)

4 394 Vol 62, 2004 V(1) O(4) (3) V(5) V(6) (12) B (6) O(27) (6) C(7) N(7) (9) V(1) V(6) (11) V(6) O(18) (4) B (6) O(2) # (6) C(7) C(8) (10) V(1) V(2) (11) V(6) O(4) (3) B (7) O(27) (6) C(8) N(8) (9) V(2) O(6) (4) V(6) O(14) (3) B (7) O(29) (6) C(9) N(9) (13) V(2) O(8) (4) V(6) O(5) (3) B (7) O(28) (7) C(9) C(10) (14) V(2) O(4) (3) V(6) O(17) (4) B (8) O(30) (6) C(10) N(10) (14) V(2) O(3) (3) B (1) O(20) (7) B (8) O(13) (7) N(1) Cu(1) N(2) 85 1 (2) O(8) V(4) O(13) (15) C(4) C(3) N(3) (7) N(1) Cu(1) N(3) (2) O(12) V(4) O(14) (18) C(4) C(3) Cu(1) 76 8 (5) N(2) Cu(1) N(3) 96 4 (2) O(11) V(4) O(14) (15) N(3) C(3) Cu(1) 42 8 (3) N(1) Cu(1) N(4) 94 6 (2) O(8) V(4) O(14) (14) C(3) C(4) N(4) (7) N(2) Cu(1) N(4) (3) O(13) V(4) O(14) (14) C(3) C(4) Cu(1) 73 9 (5) N(3) Cu(1) N(4) 84 0 (3) V(3) V(4) V(5) (3) N(4) C(4) Cu(1) 42 1 (3) N(1) Cu(1) OW (18) O(15) V(5) O(13) (17) N(5) C(5) C(6) # (5) N(2) Cu(1) OW (2) O(15) V(5) O(17) (17) N(5) C(5) Cu(2) 41 5 (3) N(3) Cu(1) OW (2) O(13) V(5) O(17) (15) C(6) # 1 C(5) Cu(2) 74 1 (4) N(4) Cu(1) OW (2) O(15) V(5) O(14) (17) N(6) C(6) C(5) # (5) N(1) Cu(1) O(1) (17) O(13) V(5) O(14) (14) N(6) C(6) Cu(2) 41 8 (2) N(2) Cu(1) O(1) 87 9 (2) O(17) V(5) O(14) (14) C(5) # 1 C(6) Cu(2) 75 3 (4) N(3) Cu(1) O(1) 86 1 (2) O(15) V(5) O(16) (17) N(7) C(7) C(8) (6) N(4) Cu(1) O(1) 92 0 (2) O(13) V(5) O(16) (14) N(7) C(7) Cu(3) 41 8 (3) OW1 Cu(1) O(1) (14) O(17) V(5) O(16) (14) C(8) C(7) Cu(3) 74 9 (4) N(6) Cu(2) N(6) # O(14) V(5) O(16) (14) N(8) C(8) C(7) (6) N(6) Cu(2) N(5) # (19) V(6) V(5) V(4) (3) N(8) C(8) Cu(3) 42 3 (3) N(6) Cu(2) N(5) 95 5 (2) O(18) V(6) O(4) (19) C(7) C(8) Cu(3) 74 8 (4) N(5) # 1 Cu(2) N(5) (1) O(18) V(6) O(14) (18) N(9) C(9) C(10) (8) N(6) Cu(2) OW2 # (18) O(4) V(6) O(14) (15) N(9) C(9) Cu(4) 41 1 (3) N(6) # 1 Cu(2) OW2 # (18) O(18) V(6) O(5) (18) C(10) C(9) Cu(4) 72 8 (6) N(5) # 1 Cu(2) OW2 # (18) O(4) V(6) O(5) (14) N(10) C(10) C(9) (8) N(5) Cu(2) OW2 # (18) O(14) V(6) O(5) (16) N(10) C(10) Cu(4) 43 4 (4) N(6) Cu(2) OW (18) O(18) V(6) O(17) (19) C(9) C(10) Cu(4) 77 0 (6) N(5) Cu(2) OW (18) O(4) V(6) O(17) (16) C(1) N(1) Cu(1) (4) OW2 # 1 Cu(2) OW O(14) V(6) O(17) (14) C(2) N(2) Cu(1) (4) N(7) # 2 Cu(3) N(7) (5) O(5) V(6) O(17) (15) C(3) N(3) Cu(1) (5) N(7) # 2 Cu(3) N(8) # (2) V(1) V(6) V(5) (4) C(4) N(4) Cu(1) (5) N(7) Cu(3) N(8) # (2) O(20) B (1) O(21) (5) C(5) N(5) Cu(2) (4) N(7) # 2 Cu(3) N(8) 96 1 (2) O(20) B (1) O(19) (5) C(6) N(6) Cu(2) (3) N(8) # 2 Cu(3) N(8) (2) O(21) B (1) O(19) (5) C(7) N(7) Cu(3) (4) N(7) # 2 Cu(3) O(12) (17) O(22) B (2) O(21) (4) C(8) N(8) Cu(3) (4) N(7) Cu(3) O(12) (17) O(22) B (2) O(7) (4) C(9) N(9) Cu(4) (5) N(8) # 2 Cu(3) O(12) (19) O(21) B (2) O(7) (4) C(10) N(10) Cu(4) (6) N(8) Cu(3) O(12) (19) O(22) B (2) O(16) # (4) V(1) O(1) Cu(1) (2) O(12) Cu(3) O(12) # O(21) B (2) O(16) # (4) B (8) # 4 O(2) B (6) # (3) N(9) Cu(4) N(9) # (19) O(7) B (2) O(16) # (4) B (8) # 4 O(2) V(1) (3) N(9) Cu(4) N(10) 84 2 (3) O(22) B (3) O(23) (4) B (6) # 4 O(2) V(1) (3) N(9) Cu(4) N(10) # (3) O(22) B (3) O(17) # (4) B (9) # 4 O(3) V(2) (3) N(10) Cu(4) N(10) # (2) O(23) B (3) O(17) # (4) B (9) # 4 O(3) V(1) (3) N(9) Cu(4) O(9) (18) O(22) B (3) O(10) (4) V(2) O(3) V(1) (15) N(10) Cu(4) O(9) 88 9 (2) O(23) B (3) O(10) (4) V(6) O(4) V(2) (2) N(10) # 3 Cu(4) O(9) 91 1 (2) O(17) # 4 B (3) O(10) (4) V(6) O(4) V(1) (15)

5 No 4 : H 3 {[ Cu(en) 2 ] 5 [ (VO) 12 O 6 B 18 O 42 ]} 395 N(9) Cu(4) O(9) # (18) O(23) B (4) O(25) (5) V(2) O(4) V(1) (15) O(9) Cu(4) O(9) # (1) O(23) B (4) O(24) (5) B (5) # 4 O(5) V(1) (3) O(1) V(1) O(5) (18) O(25) B (4) O(24) (5) B (5) # 4 O(5) V(6) (3) O(1) V(1) O(3) (19) O(26) B (5) O(25) (4) V(1) O(5) V(6) (16) O(5) V(1) O(3) (16) O(26) B (5) O(5) # (4) B (2) O(7) V(2) (3) O(1) V(1) O(2) (18) O(25) B (5) O(5) # (4) B (2) O(7) V(3) (3) O(5) V(1) O(2) (14) O(26) B (5) O(10) (4) V(2) O(7) V(3) (15) O(3) V(1) O(2) (14) O(25) B (5) O(10) (4) V(2) O(8) V(4) (19) O(1) V(1) O(4) (18) O(5) # 4 B (5) O(10) (4) V(2) O(8) V(3) (15) O(5) V(1) O(4) (14) O(26) B (6) O(11) (4) V(4) O(8) V(3) (16) O(3) V(1) O(4) (14) O(26) B (6) O(27) (4) V(3) O(9) Cu(4) (2) O(2) V(1) O(4) (15) O(11) B (6) O(27) (4) B (5) O(10) B (3) (4) V(6) V(1) V(2) (3) O(26) B (6) O(2) # (4) B (5) O(10) V(3) (3) O(6) V(2) O(8) (19) O(11) B (6) O(2) # (4) B (3) O(10) V(3) (3) O(6) V(2) O(4) (19) O(27) B (6) O(2) # (4) B (6) O(11) V(3) (3) O(8) V(2) O(4) (15) O(27) B (7) O(29) (5) B (6) O(11) V(4) (3) O(6) V(2) O(3) (19) O(27) B (7) O(28) (5) V(3) O(11) V(4) (17) O(8) V(2) O(3) (16) O(29) B (7) O(28) (4) V(4) O(12) Cu(3) (2) O(4) V(2) O(3) (14) O(30) B (8) O(13) (4) B (8) O(13) V(5) (3) O(6) V(2) O(7) (19) O(30) B (8) O(29) (4) B (8) O(13) V(4) (3) O(8) V(2) O(7) (14) O(13) B (8) O(29) (4) V(5) O(13) V(4) (17) O(4) V(2) O(7) (16) O(30) B (8) O(2) # (4) V(6) O(14) V(4) (19) O(3) V(2) O(7) (14) O(13) B (8) O(2) # (4) V(6) O(14) V(5) (15) V(1) V(2) V(3) (4) O(29) B (8) O(2) # (4) V(4) O(14) V(5) (16) O(9) V(3) O(11) (19) O(30) B (9) O(20) # (4) B (9) O(16) B (2) # (4) O(9) V(3) O(7) (19) O(30) B (9) O(3) # (4) B (9) O(16) V(5) (3) O(11) V(3) O(7) (15) O(20) # 4 B (9) O(3) # (4) B (2) # 4 O(16) V(5) (3) O(9) V(3) O(8) (18) O(30) B (9) O(16) (4) B (3) # 4 O(17) V(6) (3) O(11) V(3) O(8) (15) O(20) # 4 B (9) O(16) (4) B (3) # 4 O(17) V(5) (3) O(7) V(3) O(8) (14) O(3) # 4 B (9) O(16) (4) V(6) O(17) V(5) (15) O(9) V(3) O(10) (18) O(32) B (10) O(31) (10) B (1) O(20) B (9) # (4) O(11) V(3) O(10) (14) O(32) B (10) O(33) (10) B (1) O(21) B (2) (4) O(7) V(3) O(10) (14) O(31) B (10) O(33) (10) B (3) O(22) B (2) (4) O(8) V(3) O(10) (14) N(1) C(1) C(2) (6) B (4) O(23) B (3) (4) V(2) V(3) V(4) (3) N(1) C(1) Cu(1) 42 5 (3) B (4) O(25) B (5) (4) O(12) V(4) O(11) (18) C(2) C(1) Cu(1) 75 1 (4) B (5) O(26) B (6) (4) O(12) V(4) O(8) (18) N(2) C(2) C(1) (6) B (7) O(27) B (6) (4) O(11) V(4) O(8) (15) N(2) C(2) Cu(1) 43 0 (3) B (7) O(29) B (8) (4) O(12) V(4) O(13) (18) C(1) C(2) Cu(1) 74 2 (4) B (9) O(30) B (8) (4) O(11) V(4) O(13) (15) Symmetry codes : # 1 - x + 1, - y, - z + 1; # 2 - x - 1, - y + 1, - z + 1 ; # 3 - x, - y + 2, - z + 1 ; # 4 - x, - y + 1, - z + 1 {[ Cu ( en) 2 ] 5 [ ( VO) 12 O 6 B 18 2 [VO 5 ],6 V O 42 ]} 3 - [ H 2 O ] [ (VO) 12 O 6 B 18 O 42 ] 13 - [ H 2 O], ; (Figure 1),B 18 O B ( 3 2O) V 60, V O t V 6 O 18 (, 6 3 2O 2 B V 6,V O t (4) (3) 1 V, 3 2O B (6) (6) nm, 3 2 nm, 6 3 2O 3 V, 3 2O V O V (3) (3) nm ; O (3) ( 3) nm O V O ( 14) B 2 V, 3 2O B (7) (6) (14), V O V (15) (2) B 18 nm, 3 2O V (3) (4) nm) V 6 O 18 6 [ B 3 O 7 ] ( Figure 2 ( b) ), (Figure 2 (a) ),V [ VO 5 ],6 [ B 3 O 7 ],

6 396 Vol 62, [ (VO) 12 O 6 B 12 O 42 ] 13 - [ H 2 O] (4) (4) nm ; Cu (3) Cu (4) Figure 1 The structure of the title compound s anion cluster [ (VO) 12 2 O 6 B 18 O 42 ] 13 - [ H 2 O] [B 3 O 7 ],2 B, B, 4 O B B O (6) (6) nm,o B O 10517(4) (4) O B B O (7) (7) nm, O B O ( 4 ) ( 5 ) B O B ( 4 ) (4), B O V (3) (3), nm,cu, 2, 3 Cu (2), [ Cu (en) 2 ( H 2 O) 2 ] 2 + ;Cu (1) [V 6 O 18 ], Cu (1) O 2 [ V 6 O 18 ] Cu 2 +, Cu O, Cu (3) O (12) Cu (4) O(9) (4) (4) nm,, [ V 12 B 18 O 60 ] Cu ( 3) [ Cu(en) 2 ] 2 + a, b Cu (4) [ Cu (en) 2 ] 2 +, c (Figure 3), nm, nm, Cu (2) [ Cu ( en) 2 ( H 2 O) 2 ] 2 + [B (OH) 3 ] 3 Figure 3 The packing of the title compound with water moleculars, [B (OH) 3 ] and some [ Cu(en) 2 ] are omitted for clarity 2 V 6 O 18 (a) B 18 O 42 (b) Figure 2 Veiw of V 6 O 18 ring (a) and B 18 O 42 ring (b) [8,9] : V 4145, V V ;, V V 7 5, [B (OH) 3 ],B 3 O 360, B O [ (14) (14) nm,,9]

7 No 4 : H 3 {[ Cu(en) 2 ] 5 [ (VO) 12 O 6 B 18 O 42 ]} 397 B [ 2 ] [ Zn ( en) 2 ] 6 2 [ (VO) 12 O 6 B 18 O 39 (OH) 3 ] 13H 2 O, ph 8, ph = , [ Cu (en) 2 ] 2 + [ Zn (en) 2 ] 2 +, [ Zn ( en) 2 ] 2 + [ Cu(en) 2 ] 2 +,, cm - 1 V O, 950 cm - 1 V O t (O t ), cm - 1 V O b,c V (O b,c ) 1042 cm cm - 1 B O 4, B O 1356 cm cm - 1, cm - 1 Figure 4 The fluorescent spectra of the compound ( - NH) cm - 1 O H, cm - 1 V O, 955 cm - 1 V O t,v O b,c V 866 cm cm - 1,, 372 cm - 1 Raman V O B O nm 340 nm 2, (O t V) (O b,c 2 7 V), 570 nm, [ Cu(en) 2 ] Cu 2 + TGA (Figure 6), 29 d2d, %, ( 9148 %) ; %, nm, 415nm (Figure 4), O V 310 nm 415 nm, F ( t) = B 1 exp ( - t/ 1 ) + B 2 exp ( - t/ 2 ) ( B 1 = 53119, B 2 = 34128) 1 = 1178 ns 2 = ns, : en, [ Cu(en) 2 ] en 2 6 ESR GHz, ( ) Gauss, ( Figure 5),, g , Figure 6 The TGA diagram of the compound V 4 + Cu 2 +, V 4 + ESR 33 Gauss, - 5 ESR Figure 5 ESR of the compound en ( %), ,, 6 TGA

8 398 Vol 62, 2004 References 1 M ller, A ; Peters, F ; Pope, M T Chem Rev 1998, 98, Zhang, L2R ; Shi, Z ; Yang, G2Y ; Chen, X2M ; Feng, S 2H J Solid State Chem 1999, 148, Sevov, S C Angew Chem, Int Ed Engl 1996, 35, Rijssenbeek, J T ; Rose, D J ; Haushalter, R C ; Zubieta, J Angew Chem, Int Ed Engl 1997, 36, Lin, Z2H ; Zhang, H2H ; Huang, C2C ; Sun, R2Q ; Yang, Q 2Y ; Wu, X2Y Chin J Struct Chem 2003, 22 (6), in press (,,,,,,, 2004, 23 (1), ) 6 Sheldrick, G M SHELXS297, Program for Crystal Structure Solution, University of Gottingen, Germany, Sheldrick, G M SHELXS297, Program for Crystal Structure Refinement, University of Gottingen, Germany, Brown, I D ; Altermatt, D Acta Crystallogr 1985, B41, Brown, I D ; Wu, K K Acta Crystallogr 1976, B32, 1950 (A ZHAO, X J ; LU, Z S )

9 No 4 Graphical Abstract Study on Thermochemistry and Thermal De2 composition Kinetics of Ternary Solid2State Complex of Gadolinium Chloride with L2Tyro2 sine and Glycine ZHANG, Zhong2Hai ; KU, Zong2Jun ; XIA, Fei ; LIU, Yi ; LI, Hui2Rong ; HU, Yan2Jun ; ZHAO, Shun2Sheng ; QU, Song2Sheng Acta Chimica Sinica 2004, 62 (4), 386 Hydrothermal Synthesis, Crystal Structure and Properties of Polyoxovanadium Borate H 3 {[ Cu( en) 2 ] 5 [ ( VO) 12 O 6 B 18 O 42 ] } [ B( OH) 3 ] 2 16 H 2 O Using a solution2reaction isoperibol calorimeter, the molar enthalpy of reaction for the follow2 ing reaction, GdCl 3 6H 2 O (s) + Tyr (s) + 3Gly ( s) = Gd ( Tyr) ( Gly) 3 Cl 3 3H 2 O ( s) + 3H 2 O (l), was determined to be ( ) kj mol - 1 at K The standard molar enthalpy of formation of Gd( Tyr) ( Gly) 3 Cl 3 3H 2 O ( s) at K was derived as - ( ) kj mol - 1 The kinetics of thermal decomposition of the complex was studied by TG, DTG and DTA LIN, Zhi2Hua ; ZHANG, Han2Hui ; HUANG, Chang2Cang ; SUN, Rui2Qing ; CHEN, Yi2Ping ; WU, Xiao2Yuan Acta Chimica Sinica 2004, 62 (4), 391 In the structure of the compound, there is a ring of B 18 O 42 sandwiched between two vanadi2 um2oxygen clusters V 6 O 18 by eighteen B ( 3 2O) V bonds, and the anion clusters [ (VO) 12 O 6 B 18 O 42 ] 13 - are connected through four [ Cu(en) 2 ] 2 + by the static electronic in2 teraction Thus, the complex was extended to an infinite two2dimensional network structure, with size of the hole amounting to nm Synthesis of 2Cyclodextrin2o2vanillin Benzoylhydrazone and Its Application TANG, Bo ; ZHANG, Li2Li ; ZHANG, Jie ; WANG, Xu ; CHEN, Zhen2Zhen ; WANG, Hong2Jian ; WU, Chang2Ju Acta Chimica Sinica 2004, 62 (4), 399 A novel host molecular probe of 2cyclodextrin2o2vanillin benzoylhydrazone ( 2CDP2OVBH) was synthesized, and the fluorescent excitation ( a) and emission spectra ( b) were deter2 mined It was indicated that the complex of 2CDP2OVBH2Al 3 + was superior to those of OVBH2Al 3 + and 2CDP + OVBH + Al 3 + in the spectrofluorimetric determination of alumini2 um