Syntheses, Crystal Structures, Magnetic and Near-infrared Luminescence Properties of 3d−4f Coordination Polymers Cu₂Pr₂, Cu₂Eu₂ and Cu₄Tb₂

Abstract

Three new 3d−4f heterometallic coordination polymers(CPs), namely, [Pr₂(CuL)₂(nipt)₃(H₂O)]·2H₂O (Cu₂Pr₂, 1), [Eu₂(CuL)₂(nipt)₃(H₂O)]·2H₂O(Cu₂Eu₂, 2) and [Tb₂(CuL)₄(nipt)₃]·8.3H₂O(Cu₄Tb₂, 3)(CuL, H₂L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien; nipt2-=5-nitroisophthalate) were obtained by a solvothermal method and structurally characterized by single-crystal X-ray diffraction analyses, elemental analyses, Fourier transform infrared spectra and ultraviolet visible absorption spectra. In Cu₂Pr₂ and Cu₂Eu₂, μ ₃-bridged and μ ₅-bridged nipt^2- ligands alternately linked three Ln³⁺ and five metal ions(three Ln³⁺ and two Cu²⁺ ions) to generate a 2D heterometallic framework with 3,3,4,5-connected (3.4.5)(3².4².5.63.7²)(4².6³.8)(4².6) topology. In Cu₄Tb₂, μ₂-bridged and μ₄-bridged nipt^2- ligands alternately connected two Tb³⁺ and four metal ions(two Tb³⁺ and two Cu²⁺ ions) by carboxylating into a corrugated heterometallic 2D layer with 3-connected (63) topology. The magnetic properties of Cu₂Pr₂ and Cu₂Eu₂ were also discussed, the results show that both CPs have a weak antimagnetic interaction. Moreover, the near-infrared luminescence properties of Cu₂Pr₂ and Cu₂Eu₂ were also studied.

Keywords

Heterometallic coordination polymer / Crystal structure / Magnetic property

References

[1] Chen T H, Wang L, Trueblood J V, Grassian V H. J. Am. Chem. Soc., 2016, 138: 9646.

[2] Bunck D N, Dichtel W R. Chem. Eur. J., 2013, 19: 818.

[3] Ferrer B, Alvaro M, Baldovi H G, Reinsch H, Stock N. Chem. Phys. Chem., 2014, 15: 924.

[4] Ma D Y, Li Z, Xiao J X, Guo H F, Liu B L, Liu J Q. Inorg. Chem., 2015, 54: 6719.

[5] Hu H. C., Kang X. M., Cao C. S., Cheng P., Zhao P. B., Chem. Commun., 2015, 51(54), 10850

[6] Liu W, Dai X, Xie J, Silver M A, Zhang D, Chai Z F, Wang S A. ACS Appl. Mater. Interfaces, 2018, 10: 4844.

[7] Malaestean L L, Meliha K A, Ellern A, Leusen J V, Baca H S, Kogerler P. Cryst. Growth Des., 2012, 12: 1593.

[8] Binnemans K. Chem. Rev., 2009, 109: 4283.

[9] Peng J B, Zhang Q C, Kong X J, Zheng J M. J. Am. Chem. Soc., 2012, 134: 3314.

[10] Stamatatos T C, Teat S J, Wernsdorfer W, Christou G. Angew. Chem., Int. Ed., 2009, 48: 521.

[11] Benelli C, Gatteschi D. Chem. Rev., 2002, 102: 2369.

[12] Guo F S, Chen Y C, Liu J L, Leng J D, Meng Z S, Vrabel P, Orendac M, Tong M L. Chem. Commun., 2012, 48: 12219.

[13] Boyer J C, Carling C J, Gates B D, Branda N R. J. Am. Chem. Soc., 2010, 132: 15766.

[14] Trivedi E R, Eliseeva S V, Jankolovits J, Olmstead M M, Petoud S, Pecoraro V L. J. Am. Chem. Soc., 2014, 136: 1526.

[15] Zhang Z M, Pan L Y, Lin W Q, Leng J D, Guo F S. Chem. Commun., 2013, 49: 8081.

[16] Kahn M L, Lecante P, Verelst M, Mathonieìe C, Kahn O. Chem. Mater., 2000, 12: 3073.

[17] Sun Y. Q., Wang J., Fan L. L., Gao D. Z., Chem. Res. Chinese Universities, 2009, 25(2), 279

[18] Sun Y Q, Xu Y Y, Gao D Z, Zhang G Y, Liu Y X, Wang J, Liao D Z. Dalton Tran., 2012, 41: 5704.

[19] Xin N, Sun Y Q, Zheng Y F, Gao D Z, Zhang G Y. J. Solid State Chem., 2016, 243: 267.

[20] Black D S C, Corrie H. Inorg. Nucl. Chem. Lett., 1976, 12: 65.

[21] Nakamoto K. Infrared, Raman Spectra of Inorganic and Coordination Compounds, 1997 5th Ed. New York: John Wiley.

[22] Lampeka Y D, Gavrish S P. Polyhedron, 2000, 19: 2533.

[23] Chorazy S, Sieklucka B, Ohkoshi S I. Cryst. Growth Des., 2016, 16: 4918.

[24] Chorazy S, Arczynski M, Nakabayashi K, Sieklucha B, Ohkoshi S I. Inorg. Chem., 2015, 54: 4724.

[25] Trivedi E R, Eliseeva S V, Jankolovits J, Olmstead M M, Petoud S, Pecoraro V L. J. Am. Chem. Soc., 2014, 136: 1526.

[26] Aboshyan-Sorgho L, Nozary H, Aebischer A, Bünzli J C G, Morgantini P Y, Kittilstved K R, Hauser A, Eliseeva S V, Petoud S, Piguet C. J. Am. Chem. Soc., 2012, 134: 12675.

[27] Kahn O. Molecular Magnetism, 1993, New York: VCH.

[28] Xu J X, Ma Y, Liao D Z, Xu G F, Tang J K, Wang C, Zhou N, Yan S P, Cheng P, Li L C. Inorg. Chem., 2009, 48: 8890.