A new cobalt(II) coordination polymer (CP), poly[[bis[μ-4-(4-carboxylatophenoxy)benzene-1,3-dicarboxylato-κO:O:O:O:O:O]bis(1,10-phenanthroline-κN,N')tricobalt(II)] 0.72-hydrate], {[Co(CHO)(CHN)]·0.72HO}, (I), is constructed from Co ions and 4-(4-carboxyphenoxy)isophthalate (cpoia) and 1,10-phenanthroline (phen) ligands. Based on centrosymmetric trinuclear [Co(phen)(COO)] secondary building units (SBUs), the structure of (I) is a three-dimensional CP with a (3,6)-connected net and point symbol (4.6)(4.6.8.10). The positions of four [Co(phen)(COO)] SBUs and four cpoia ligands reproduce a Chinese-knot-shaped arrangement along the ab plane. (I) has been characterized by single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD) and thermostability analysis. It shows a good thermal stability from room temperature to 673 K. In addition, the temperature dependence of the magnetic properties was measured.
A new mononuclear europium complex incorporating the (+)‐di‐p‐toluoyl‐d‐tartaric acid (d‐H2DTTA) ligand, namely, catena‐poly[tris{μ2‐3‐carboxy‐2,3‐bis[(4‐methylphenyl)carbonyloxy]propanoato}tris(methanol)europium(III)], [Eu(C20H17O8)3(CH3OH)3]n, (I), has been synthesized and characterized by IR spectroscopy, elemental analysis, powder X‐ray diffraction and single‐crystal X‐ray diffraction analysis. The structure analysis indicates that complex (I) crystallizes in the trigonal space group R3 and exhibits an infinite one‐dimensional chain structure, in which the Eu3+ ion is surrounded by six O atoms from six d‐HDTTA− ligands and three O atoms from three coordinated methanol molecules, thus forming a tricapped trigonal prism geometry. The d‐H2DTTA ligand is partially deprotonated and adopts a μ1,6‐coordination mode via two carboxylate groups to link adjacent Eu3+ ions, affording an infinite one‐dimensional propeller‐shaped coordination polymer chain along the c axis, with an Eu…Eu distance of 7.622 (1) Å. Moreover, C—H…π interactions lead to the formation of helical chains running along the c axis and the whole structure displays a snowflake pattern in the ab plane. The circular dichroism spectrum confirms the chirality of complex (I). The solid‐state photoluminescence properties were also investigated at room temperature and (I) exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.63, 0.32), with a reasonably long lifetime of 0.394 ms, indicating effective energy transfer from the ligand to the metal centre. In addition, a magnetic investigation reveals single‐ion magnetic behaviour. The spin‐orbit coupling parameter (λ) between the ground and excited states is fitted to be 360 (2) cm−1 through Zeeman perturbation. Therefore, complex (I) may be regarded as a chiral optical‐magneto bifunctional material.
Two new isostructural complexes, namely, poly[aqua[μ3-2-(4-carboxyphenoxy)terephthalato-κ3 O 1:O 4:O 4′](1,10-phenanthroline-κ2 N,N′)cobalt(II)], [Co(C15H8O7)(C12H8N2)(H2O)] n or [Co(μ3-Hcpota)(phen)(H2O)] n , I, and poly[aqua[μ3-2-(4-carboxyphenoxy)terephthalato-κ3 O 1:O 4:O 4′](1,10-phenanthroline-κ2 N,N′)nickel(II)], [Ni(C15H8O7)(C12H8N2)(H2O)] n or [Ni(μ3-Hcpota)(phen)(H2O)] n , II, have been synthesized by solvothermal reactions. Complexes I and II were fully characterized by IR spectroscopy, elemental analyses, thermogravimetric analyses, and powder and single-crystal X-ray diffraction. They both present two-dimensional structures based on [M 2(μ-COO)2]2+ (M = CoII or NiII) dinuclear metal units with a fes topology and a vertex symbol (4·82). Interestingly, the positions of the two dimeric metal motifs and the two partially deprotonated Hcpota2− ligands reproduce regular flying butterfly arrangements flipped upside down and sharing wings in the ab plane. Magnetic studies indicate antiferromagnetic interactions (J = −5.21 cm−1 for I and −11.53 cm−1 for II) in the dimeric units, with Co...Co and Ni...Ni distances of 4.397 (1) and 4.358 (1) Å, respectively, that are related to double syn–anti carboxylate bridges.
A new coordination polymer (CP), namely, poly[[diaquatris[μ2-1,4-bis(1H-imidazol-1-yl)benzene]bis[μ6-4-(2,4-dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate], {[Co4(C16H6O9)2(C12H10N4)3(H2O)2]·6H2O} n , has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. It presents a three-dimensional (3D) structure based on tetranuclear CoII secondary building units (SBUs) with a tfz-d net and point symbol (43)2(46·618·84). The 4-(2,4-dicarboxyphenoxy)phthalic acid (H4dcppa) ligands are completely deprotonated and link {Co4(COO)4}4− SBUs into two-dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4-bis(1H-imidazol-1-yl)benzene (bib) ligands, giving rise to a 3D supramolecular architecture. Interestingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexameric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail.
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