KURNAKOV INSTITUTE OF GENERAL AND INORGANIC CHEMISTRY

KURNAKOV INSTITUTE OF GENERAL AND INORGANIC CHEMISTRY RUSSIAN ACADEMY OF SCIENCES E. S. Bazhina, M. A. Kiskin, G. G. Aleksandrov, A. A. Sidorov, I. L. Eremenko POLYNUCLEAR ARCHITECTURES BASED ON FRAGMENT OF OXOVANADIUM(IV) AND TWO CHELATED SUBSTITUTED MALONIC ACID ANIONS ICFM-2015 г. Novosibirsk, October 5 -9, 2015

PROPERTIES AND PROSPECTS OF USING DESIGN OF UNUSUAL METAL-ORGANIC MAGNETIC FRAMEWORK PROPERTIES SOLIDS [I. Gil de Muro et al, (MOF) PEROVSKITE-RELATED Polyhedron, 2004, 23, 929; [B. Dey et al, C. Ruiz-Perez et al, Inorg. Chim. Acta, 2010, 363, 981] MIXED METAL OXIDES Inorg. Chim. Acta, 2000, 298, 202] [I. Gil de Muro et al, Inorg. Chem. , 1998, 37, 3243; I. Gil de Muro et al, J. Chem. Soc. , Dalton Trans. , 2000, 3360] HETEROMETALLIC PHOTOLUMINESCENT PROPERTIES POLYNUCLEAR COMPOUNDS NANOSTRUCTURED ANTITUMOR AND ANTIDIABETIC METAL OXIDES PROPERTIES HETEROGENEOUS [D. Ghoshal et al, ANTIBACTERIAL AND ANTIFUNGAL CATALYSTS Inorg. Chim. Acta, 2005, 358, 1027] ACTIVITIES [D. Lebowhl, R. Canetta, Eur. J. Cancer, 1998, 34, 1522; M. Sutradhar et al, Inorg. Chim. Acta, 2011, 368, 13]

DICARBOXYLIC ACIDS OXALIC ACID MALONIC ACID SUCCINIC ACID GLUTARIC ACID ADIPIC ACID PIMELIC ACID SUBERIC ACID AZELAIC ACID …

OBJECTS OF THE INVESTIGATION VO 2+ LIGANDS CATION Cyclopropane- Dimethylmalonic Cyclobutane- Butylmalonic -1, 1 -dicarboxylic acid acid (H 2 Cpdc) (H 2 Me 2 mal) acid (H 2 Cbdc) (H 2 Bumal) CATIONS OF HETEROMETALS s-elements d-elements Li+, Na+, K+ Mn 2+, Co 2+, Ni 2+, f-elements Ca 2+, Sr 2+, Ba 2+ and Mg 2+ Cu 2+, Zn 2+, Cd 2+ La 3+ and lantanides(III)

COMPOUNDS (VIVO)-Ba C. N. = 6 C. N. = 5 VOSO 4+ 2 H 2 L + 2 Ba(OH)2 L = Cpdc L = Me 2 mal H 2 O L = Bumal {[Ba 2(VO)2 (Cpdc)4(H 2 O)8]· 2 H 2 O}n {[Ba 3(VO)3(Bumal)6(H 2 O)13]· 4 H 2 O}n (yield 58. 9 %) {[Ba(VO)(Me 2 mal)2(H 2 O)]·H 2 O}n (yield 57. 7 %) (yield 40. 1 %) 3 D-FRAMEWORK 2 D-LAYERS V=O 1. 58(2)– 1. 610(7) Å V–O (H 2 O) 2. 212(7)– 2. 37(2) Å V–O (L) 1. 954(5)– 2. 02(2) Å E. S. Bazhina, M. E. Nikiforova, G. G. Aleksandrov at al, Russ. Chem. Bull. , Int. Ed. , 2011, 60, 797. Ba–O 2. 61(2)– 3. 01(2) Å E. S. Bazhina, G. G. Aleksandrov, A. S. Bogomyakov et al, Polyhedron, 2013, 77, 47.

COMPOUNDS (VIVO)-Sr H 2 O VOSO 4+ 2 H 2 L + 2 Sr(OH)2 L = Cpdc L = Me 2 mal L = Cbdc L = Bumal [Sr(VO)(Cpdc)2(H 2 O)6]n {[Sr 3(VO)3(Bumal)6(H 2 O)12]· 2 H 2 O}n (yield 59. 3 %) [Sr(VO)(Cbdc)2(H 2 O)5]n (yield 87. 6 %) (yield 58. 1 %) 1 D-CHAIN 3 D-FRAMEWORK {Sr(H 2 O)8[(VO)(Me 2 mal)2]}n (yield 41. 9 %) 2 D-LAYERS BRIDGING 1 D-CHAIN COORDINATION! V=O 1. 584(5)– 1. 612(8) Å V–O (H 2 O) 2. 275(6)– 2. 439(5) Å V–O (L) 1. 966(5)– 2. 035(6) Å Sr–O 2. 488(3)– 2. 816(5) Å E. S. Bazhina, M. E. Nikiforova, G. G. Aleksandrov at al, Russ. Chem. Bull. , Int. Ed. , 2011, 60, 797. E. S. Bazhina, G. G. Aleksandrov, A. A. Sidorov, I. L. Eremenko, Russ. J. Coord. Chem. , 2015, 41, 730.

COMPOUNDS (VIVO)-Sr: UNUSUAL 2 D COORDINATION POLYMER H 2 O VOSO 4+2 H 2 Me 2 mal + 2 Sr(OH)2 {Sr(H 2 O)8[(VO)(Me 2 mal)2]}n (yield 41. 9 %) ONLY BRIDGING COORDINATION! HYDROGEN BONDING BETWEEN LAYERS 2 D-LAYER O(H 2 O)…O(Me 2 mal) 2. 70(2)– 2. 82(2) Å V=O 1. 580(5) Å V–O (Me 2 mal) 1. 965(9)– 2. 03(1) Å Sr…O (H 2 O) 2. 58(1) Å– 2. 67(1) Å V…V (in layer) 8. 367(4), 8. 379(5) Å V…V 10. 227(3) Å (between layers) E. S. Bazhina, M. E. Nikiforova, G. G. Aleksandrov at al, Russ. Chem. Bull. , Int. Ed. , 2012, 61, 1426.

COMPOUNDS (VIVO)-Ca VOSO 4+ H 2 L + 2 Ca(OH)2 H 2 O L = Cpdc L = Cbdc, Bumal {[Ca(VO)(Cpdc)2(H 2 O)5]·H 2 O}n {[Ca(VO)(Cbdc)2(H 2 O)4]· 2 H 2 O}n (yield 55. 4 %) (yield 35. 9 %) 1 D-CHAIN {[Ca(VO)(Bumal)2(H 2 O)5]·H 2 O}n (yield 29. 4 %) 2 D-LAYERS SIDE VIEW V=O 1. 582(2)– 1. 604(2) Å V–O (H 2 O) 2. 308(2), 2. 313(3) Å V–O (L) 1. 977(2)– 2. 014(2) Å Ca–O 2. 252(7)– 2. 716(2) Å 1 D-CHAIN E. S. Bazhina, G. G. Aleksandrov, A. A. Sidorov, I. L. Eremenko, Russ. J. Coord. Chem. , 2015, 41, 730

COMPOUNDS (VIVO)-M (M = Ca, Sr, Ba) H 2 O VOSO 4+ H 2 L + 2 M(OH)2 {[Mx(VIVO)x(L)2 x(H 2 O)y]·z. H 2 O}n L= Ca 2+ 1 D 2 D 1 D Sr 2+ 1 D 3 D 2 D Ba 2+ 3 D 2 D

COMPOUNDS (VIVO)-K VOSO 4 + 2 H 2 L +3 K 2 CO 3 L = Me 2 mal L = Bumal H 2 O L = Cbdc ? [K 4(VO)2(Cbdc)4(H 2 O)4]n ? (yield 36. 7 %) Formation of K 6[VV 10 O 28] crystals 3 D-FRAMEWORK V=O 1. 600(4), 1. 602(4) Å V–O (Cbdc) 1. 939(4)– 2. 002(4) Å K–O (H 2 O) 2. 664(5)– 2. 836(5) Å K–O (V=O) 2. 806(4), 2. 808(4) Å K–O (Cbdc) 2. 565(4)– 3. 038(4) Å

COMPOUNDS (VIVO)-Na VOSO 4 + 2 H 2 L +3 Na 2 CO 3 L = Me 2 mal L = Bumal L = Cbdc [Na 4(VO)2(Me 2 mal)4(H 2 O)]n {[Na 6(VO)3(Bumal)6(H 2 O)15]· 3 H 2 O}n [Na 2(VO)(Cbdc)2(H 2 Cbdc)(H 2 O)3]n (yield 74. 6 %) (yield 57. 9 %) (yield 26. 4 %) 2 D-LAYERS 3 D-FRAMEWORK 2 D-LAYERS V=O 1. 578(4)– 1. 603(4) Å V–O (H 2 O) 2. 272(2)– 2. 445(3) Å V–O (L) 1. 956(2)– 2. 018(3) Å Na–O 2. 272(2)– 2. 701(4) Å E. S. Bazhina, G. G. Aleksandrov, M. A. Kiskin at al, Russ. Chem. Bull. , Int. Ed. , 2014, 63, 1475

COMPOUNDS (VIVO)-Li: ROLE OF THE SOLVENT VOSO 4 + 2 H 2 L +2 Li 2 CO 3 H 2 O Et. OH L= [Li 2(VO)(Me 2 mal)2(H 2 O)(Et. OH)]n [Li 2(VO)(Me 2 mal)2]n LAYER VIEW 3 D-FRAMEWORK 2 D-LAYERS V=O 1. 545(9) Å V=O 1. 587(3) Å V–O (Me 2 mal) 1. 963(4), 1. 966(5) Å V–O (Me 2 mal) 1. 9423(19), 1. 9568(19) Å Li…O (Me 2 mal) 1. 97(1)– 2. 18(1) Å Li…O (Me 2 mal) 1. 865(4), 2. 044(6) Å Li…O E. S. Bazhina, G. G. Aleksandrov, M. A. Kiskin at al, Russ. Chem. Bull. , Int. Ed. , 2015, in press. (H 2 O, Et. OH) 1. 955(8)– 2. 006(8) Å

COMPOUNDS (VIVO)-Li: ROLE OF THE SOLVENT VOSO 4 + 2 L +2 Li 2 CO 3 L= H 2 O Et. OH [Li 4(VO)2(Cbdc)4(H 2 O)7]n (yield 41. 9%) V=O 1. 582(2), 1. 590(2) Å V–O (Cbdc) 1. 956(2)– 1. 967(2) Å Li…O (H 2 O) 1. 797(8)– 2. 30(2) Å Li…O (Cbdc) 1. 877(4)– 2. 033(4) Å 2 D-LAYERS E. S. Bazhina, G. G. Aleksandrov, M. A. Kiskin at al, Russ. Chem. Bull. , Int. Ed. , 2015, in press.

COMPOUNDS (VIVO)-Li: ROLE OF THE SOLVENT VOSO 4 + 2 H 2 L +2 Li 2 CO 3 L= H 2 O Et. OH [Li 4(VO)2(Bumal)4(H 2 O)11] [Li 4(VO)2(Bumal)4(H 2 O)8]·H 2 O (yield 73. 1 %) (yield 61. 8 %) 2 D-LAYERS “ 0 D” – MOLECULE! V=O 1. 590(3) Å V=O 1. 582(3) Å V–O (H 2 O) 2. 349(3) Å V–O (H 2 O) 2. 393(3) Å V–O (Bumal) 2. 005(2)– 2. 016(2) Å V–O (Bumal) 1. 996(2)– 2. 009(2) Å Li…O (H 2 O) 1. 604(12)– 2. 211(14) Å Li…O (H 2 O) 1. 889(6)– 2. 319(7) Å Li…O (Bumal) 1. 917(7)– 2. 343(13) Å Li…O (Bumal) 1. 935(7)– 2. 164(7) Å E. S. Bazhina, G. G. Aleksandrov, N. N. Efimov, Russ. Chem. Bull. , Int. Ed, 2013, 62, 962. E. S. Bazhina, G. G. Aleksandrov, M. A. Kiskin at al, Russ. Chem. Bull. , Int. Ed. , 2015, in press. CRYSTAL PACKING

COMPOUNDS (VIVO)-MII (MII = Mn, Co, Cd): 1 D-POLYMERS H 2 O {[Bax(VIVO)x(L)2 x(H 2 O)y]·z. H 2 O}n + xn. MSO 4 {[M(VO)L 2(H 2 O)5]·H 2 O}n MII = Mn, Co, Cd; L = Me 2 mal, Bumal V=O 1. 581(3)– 1. 597(2) Å Co–O 2. 063(2)– 2. 173(2) Å V–O (H 2 O) 2. 317(3)– 2. 357(2) Å Mn–O 2. 134(3)– 2. 270(4) Å V–O (L) 1. 965(3)– 2. 008(2) Å Cd–O 2. 239(3)– 2. 326(4) Å E. S. Bazhina, G. G. Aleksandrov, A. S. Bogomyakov et al, Polyhedron, 2013, 77, 47.

COMPOUNDS (VIVO)-MII (MII = Mn, Co, Ni, Cd) WITH CBDC L= Solid of unknown H 2 O composition VOSO 4+MSO 4 + 2 H 2 L + 2 Ba(OH)2 {[Cd(VO)L 2(H 2 O)5]·H 2 O}n +MSO 4 +Cd. SO 4 (yield 48. 6%) +MSO 4 H 2 O, Et. OH M = Mn: yield 54. 7 % monocrystals M = Co: yield 78. 9 % [M(VO)(Cbdc)2(Et. OH)2(H 2 O)3]n M = Ni: yield 40. 4 % M = Mn, Co, Ni 1 D-CHAIN V=O 1. 599(5) Å Cd–O (L) 2. 256(4) Å V–O (H 2 O) 2. 356(5) Å Cd–O (H 2 O) 2. 234(5)– 2. 417 (3) Å V–O (L) 1. 975(3), 2. 016(3) Å V…Cd 4. 8308(8) Å COMPLEXES Cu. II-Co. II AND Cu. II-Cd 1 D-CHAIN V=O 1. 569(2)– 1. 589(3) Å V–O(L) 1. 991(4)– 2. 028(4) Å V–O(H 2 O) 2. 260(4)– 2. 297(3) Å M–O (L) 2. 038(4) (Ni)-2. 228(2) (Mn) Å M–O (H 2 O) 2. 055(4)-2. 206(2) Å M–O (Et. OH) 2. 036(4)-2. 174(2) Å IONIC COMPLEX! 2 D-POLYMER!

COMPOUNDS (VIVO-MII) (MII = Cu, Zn) VOSO 4+MSO 4 + 2 H 2 L + 2 Ba(OH)2 M=Cu; M=Zn; M=Zn, L=Me 2 mal, H 2 O L=Cbdc Bumal [Zn(VO)L 2(H 2 O)5]·H 2 O (yield 72. 5%) [Cu(L)(H 2 O)]n + ? [Zn(L)(H 2 O)]n + ? MOLECULAR COMPLEX 2 D-POLYMERS V=O 1. 599(1) Å V–O (H 2 O) 2. 222(1) Å V–O (Cbdc) 1. 981(1)– 2. 027(1) Å Zn–O (Cbdc) 2. 182(1), 2. 273(1) Å Zn–O (H 2 O) 2. 031(1)– 2. 063(1) Å V…Zn 3. 9528(4) Å [Cu(Me 2 mal)(H 2 O)]n FOR Cu. II – IONIC COMPLEX [Zn(H 2 O)6][Cu(Cbdc)2(H 2 O)]

COMPOUNDS (VIVO)-Mg H 2 O {[Bax(VIVO)x(L)2 x(H 2 O)y]·z. H 2 O}n + xn. Mg. SO 4 crystals unsuitable for X-ray L= 18

COMPOUNDS (VIVO)-Mg L= H 2 O [K 4(VO)2(Cbdc)4(H 2 O)4]n + 2 n. Mg(NO 3)2 {[KMg 0. 5(VO)(cbdc)2(H 2 O)7]· 3 H 2 O}n (yield 52. 8 %) [K 4(VO)2(Cbdc)4(H 2 O)4]n Mg 2+ 1 D-CHAIN 3 D-FRAMEWORK Mg–O (Cbdc) 2. 094(4) Å SIDE VIEW OF THE RIBBON V=O 1. 593(3) Å Mg–O (H 2 O) 1. 931(4)-2. 238(5) Å V–O (Cbdc) 1. 992(2)– 2. 021(2) Å K…O (H 2 O) 2. 732(7)-3. 023(3) Å V–O (H 2 O) 2. 270(3) K…O (Cbdc) 2. 718(2)-2. 837(2) Å

COMPOUNDS VIVO-Ln. III H 2 O [K 4(VO)2(Cbdc)4(H 2 O)4]n + (4/3)n. Gd(NO 3)3 {[KGd(VO)2(Cbdc)4(H 2 O)9]· 3. 5 H 2 O}n L= STRUCTURE OF THE TRINUCLEAR FRAGMENT {V-Gd-V} V=O 1. 581(3), 1. 588(3) Å V–O (H 2 O) 2. 241(3), 2. 419(3) Å V–O (Cbdc) 1. 976(3)– 2. 016(3) Å Gd–O (Cbdc) 2. 355(3), 2. 443(3) Å Gd–O (H 2 O) 2. 332(3)– 2. 487(3) Å V…Gd 4. 5933(8), 6. 0050(7) Å K–O (Cbdc) 2. 739(3)-2. 965(3) Å K–O (H 2 O) 2. 708(3) Å

CONCLUSIONS Ba 2+, Sr 2+, Ca 2+ Ba 2+, Sr 2+ Sr 2+, Ca 2+ Ba 2+, Sr 2+, Ca 2+ 3 D 2 D 1 D 2 D 1 D Na+, Li+ K+, Na+, Li+ 3 D 3 D 2 D 2 D 2 D 0 D Mn 2+, Co 2+, Cd 2+ Mn 2+, Co 2+, Ni 2+, Zn 2+, Cd 2+ Mn 2+, Co 2+, Cd 2+ 1 D 0 D 1 D

ACKNOWLEDGMENT X-RAY HEADS Dr. Mikhail A. Kiskin Dr. Grigory G. Aleksandrov Prof. Igor L. Eremenko Cu. II COMPLEXES Prof. Alexey A. Sidorov FINANCIAL SUPPORT RUSSIAN COUNCIL ON ACADEMY OF GRANTS OF THE SCIENCES PRESIDENT OF RF PROJECTS №№ 13 -03 -00703, 13 -03 -12430 14 -03 -01116, Dr. Natalya V. Gogoleva 14 -03 -31292 МК-2917. 2014. 3, NSh-4773. 2014. 3

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