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Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion
Author(s) -
Zottnick Sven H.,
Daul Wiebke G.,
Kerpen Christoph,
Finze Maik,
MüllerBuschbaum Klaus
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802627
Subject(s) - lanthanide , chemistry , acetonitrile , pyridine , photoluminescence , coordination number , coordination complex , inorganic chemistry , ion , crystallography , materials science , metal , medicinal chemistry , organic chemistry , optoelectronics
New lanthanide cyanoborates were synthesized from anhydrous lanthanide chlorides and the acid H[BH 2 (CN) 2 ] in either acetonitrile or pyridine. Reactions in acetonitrile lead to three‐dimensional, anionic metal‐organic frameworks (MOFs) 3 ∞ [Ln 2 {BH 2 (CN) 2 } 9 ] ⋅ [Ln(CH 3 CN) 9 ] (Ln=Ce, Eu, Tb) which incorporate complex cations [Ln(CH 3 CN) 9 ] 3+ in the pores of the framework for charge compensation. In contrast, the reactions in pyridine result in the formation of one‐dimensional coordination polymers 1 ∞ [H(py) 2 ][LnCl 2 {BH 2 (CN) 2 } 2 (py) 2 ] ⋅ 0.5 py (Ln=Ce, Pr, py=pyridine) with [H(py) 2 ] + as counter ions for the anionic strand structure. The products show intense photoluminescence, for Ce 3+ based on 5d–4f transitions in the blue spectral region, whereas the Eu 3+ and Tb 3+ compounds exhibit characteristic photoluminescence based on 4f–4f transitions of the respective lanthanide ions. The observed photoluminescence is mainly attributed to a direct excitation of the lanthanide ions and sensitization of the lanthanide ions by the [BH 2 (CN) 2 ] − anions. These results mark the utilized borate anions as versatile building block for new coordination compounds.