Polynuclear copper(II) complexes of di-2-pyridyl ketone derivatives and tert-butylphosphonic acid: crystal structures and magnetic behaviour

Abstract

The syntheses, structural characterization, and magnetic behavior of four new copper(II) complexes derived from tert-butylphosphonic acid and di-2-pyridyl ketone with formulae [Cu{(py)(2)C(OH)(2)}](C(4)H(9)PO(3)H)(2).(H(2)O)(2) (1), [Cu(2)(mu(2)-C(4)H(9)PO(3)H){(py)(2)C(OCH(2)CH(3))O}(mu(2)-NO(3))(NO(3))(H(2)O)](n).(H(2)O)(n) (2), [Cu(4)(mu(2)-C(4)H(9)PO(3)H)(2)(mu(4)-C(4)H(9)PO(3))(2){(py)(2)C(OCH(3))O}(2)].2H(2)O (3) and Na[Cu(6)(mu(3)-C(4)H(9)PO(3))(3){(py)(2)C(OCH(3))O}(3)(mu(6)-NO(3))(NO(3))(3)] (4) (C(4)H(9)PO(3)H(2) = tert-butylphosphonic acid, (py)(2)C(OH)(2) = bis(2-pyridyl)methanediol, {(py)(2)C(OCH(2)CH(3))O}(-) = bis(2-pyridyl)ethoxymethanolato {(py)(2)C(OCH(3))O}(-) = bis(2-pyridyl)methoxymethanolato, are reported. 1 is a mononuclear compound, with tert-butylhydrogenphosphonate in the anionic form. 2 is a nitrate bridged monodimensional compound with 2.110 tert-butylhydrogenphosphonate bridging ligands. 3 is a tetranuclear compound with 2.110 tert-butylhydrogenphosphonate and 3.111 tert-butylphosphonate bridging ligands and 4 is a hexanuclear compound with 3.111 tert-butylphosphonate bridging ligands. The magnetic properties of 2-4 are reported.

CuII Frameworks from Di‐2‐pyridyl Ketone and Benzene‐1,3,5‐triphosphonic Acid

“…It appears that the presence of the bulkier R–PO 3 H – groups in 2 instead of AcO – in [Cu 4 {py 2 C(OH)O} 2 (AcO) 6 ] leads to a lengthening of the Cu ··· Cu distances within the respective [Cu 2 {(py) 2 C(OH)O}] 3+ dinuclear units by approximately 0.2 Å, resulting in a considerably larger Cu–OR–Cu angle (119.04° in 2 instead of 108.44°), which is crucial for the analysis of the different magnetic properties of the two complexes. Complexes 1 and 2 join a small family of di‐2‐pyridyl ketone/phosphonate Cu II and Ni II complexes , …”

“…A thorough investigation of the Cu II /py 2 CO/H 6 btp reaction system led to the isolation of the mononuclear complex [Cu{(py) 2 C(OH) 2 } 2 ] · H 4 btp · 1.5H 2 O ( 1 ), which forms a complex 3D hydrogen‐bonded framework, and the 2D coordination polymer {[Cu 2 {(py) 2 C(OH)O}(H 3 btp)(H 2 O)] · 6H 2 O} n ( 2 ), which is based on a new [Cu 4 ] SBU. Complexes 1 and 2 join a small family of metal (Cu II and Ni II only)/py 2 CO/phosphonate complexes , …”

“…Complexes 1 and 2 join a small family of di-2-pyridyl ketone/phosphonate Cu II and Ni II complexes. [26,[33][34][35][36] …”

“…[32] Following this approach, we isolated a series of 1D, 2D and 3D coordination polymers and hydrogenbonded frameworks in which the various forms of the py 2 CO gave rise to the formation of dinuclear Cu II complexes that served as nodes and, in combination with the bridging bi-or polycarboxylates, led to extended frameworks. Extending this approach to bridging ligands beyond bi/polycarboxylates, poly- [26,[33][34][35][36] Results and Discussion…”

Molecular Copper(II) Complexes Derived from Phosphonoacetic Acid: Crystal Structures and Magnetic Behavior

“…Usually, the mono-and dianion derivatives of the gem-diols and the monoanion of the hemiketals can bridge two or more metal ions. [28,29] In related recently published papers, [31,32] several dpk-Rphosphonic copper(II) derivatives have been reported (R = tertbutyl). Here, we report the structural characterization and the magnetic behavior of two new copper(II) dpk-Rphosphonic complexes: mononuclear [Cu{(py) 2 C(OH) 2 Figure 1).…”