The first metal (Nd3+ Mn2+, and Pb2+) coordination compounds of 3,5-dinitrotyrosine and their nonlinear optical properties

The reactions of 3,5-dinitrotyrosine (H2DNTY) with Nd(NO3)(3).6H(2)O, Mn(ClO4)(2).6H(2)O, and Pb(OAc)(2) afforded three homochiral compounds: discrete [Nd(Hdnty)(2)(NO3)(H2O)(5)].3H(2)O (1) and two- and three-dimensional coordination polymers, [Mn(HdntY)(2)] (2) and [Pb(dnty)(0.5H(2)O)] (3), respectively. The Nd atom in 1 displays a tricapped trigonal prism and supramolecular weak interactions, such as it-a stacking and H-bonds, between amino and nitro groups result in the formation of a three-dimensional network through these interactions. 2 has a two-dimensional square-grid topological net while 3 has the first three-dimensional homochiral ThSi2 net. To the best of our knowledge, these are the first metal coordination compounds with 3,5-dinitrotyrosine. Preliminary second harmonic generation (SHG) investigations indicated that 1 and 2 are SHG active with estimated responses 5 and 6 times larger than that of urea, respectively, while 3 is SHG non-active (obeying the Klainman symmetry requirement). Strong enhancement of their SHG efficiency, compared with H2DNTY, may be due to 1) the addition of a good donor-pi-acceptor organic chromophore into the compound resulting in superior qualities of both inorganic and organic materials and 2) the H-bonds that persist in them. Crystal data: 1: C18H32N7O25Nd, M-r = 890.75 g mol(-1), monoclinic, P2(1), a = 7.0179(7), b = 27.060(3), c = 8.3097(8)Angstrom, alpha = gamma = 90.00, beta = 95.646(2)degrees, V = 1570.4(3)Angstrom(3), Z = 2, rho(calcd) = 1.884 Mg M-3, R-1 = 0.0489, wR(2) = 0.1223, mu = 17.67 mm(-1), S = 0.811, Flack value = 0.003(13); 2 : C18H16N6O14Mn, M-r = 595.31 g mol(-1), orthorhombic, P2(1)2(1)2, a = 8.4381(14), b=13.639(2), c = 19.697(3)Angstrom, alpha = beta = gamma = 90.00degrees, V = 2266.9(6) Angstrom(3), Z=4, rho(calcd) = 1.744 Mg m(-3), R-1 = 0.0866, wR(2) = 0.2030, mu = 6.72 mm(-1), S = 1.095, Flack value = 0.02(6); 3:, C6H8N3O7.5Pb, M-r = 485.37g mol(-1), tetragonal, P4(1)2(1)2, a = 12.8136(12), b = 12.8136(12), c = 14.931(2), alpha = beta = gamma =90.00degrees, V = 2451.5(5) Angstrom(3), Z = 8, rho(calcd) = 1.885 Mg m(-3), R-1 = 0.0564, wR(2) = 0.1323, mu = 6.942mm(-1), S=0.878, Flack value = 0.03(2). For space group P4(3)2(1)2: R-1= 0.0672, wR(2) = 0.1656, S = 1.034, Flack value = 1.02(3); this suggests the chosen space group P4(1)2(1)2 is correct.