A Novel Three‐Dimensional Copper(II) 1,2‐Ethylenediphosphonate Framework with Channel‐like Voids

Abstract

Turquoise monoclinic single crystals of the novel three‐dimensional Cu2[μ8‐O3P(CH2)2PO3]·3.2H2O coordination polymer were prepared using the silica gel method. Space group C2/m (no. 12) with a = 1483.6(2), b = 668.44(8), c = 436.30(6) pm, β = 93.28(2)°. The Cu2+ cation is coordinated by four oxygen atoms stemming from the 1,2‐ethylenediphosphonate dianions in a square planar manner and two water molecules in the axial positions. The connection between the Cu2+ cations and the [CPO3] units from the 1,2‐ethylenediphosphonate dianions leads to layers parallel to (100), which are linked by the ethylene groups to a three‐dimensional framework with channel‐like voids. The channel‐like voids accommodate water molecules not bound to Cu2+ and extend parallel to [001] with an opening of about 550 pm × 260 pm. Magnetic measurements reveal an antiferromagnetic behavior due to a superexchange coupling between Cu2+ ions through an oxygen bridge. The UV/Vis spectrum reveals three d–d transition bands at 694, 774, and 918 nm. The compound can be fully dehydrated by thermal treatment and rehydrated by storage in ambient air.

Synthesis, Crystal Structure, and Characterization of Two Novel One- and Two-Dimensionally Polymeric Copper(II) Phosphonoacetates

“…The weak band at 2921 cm –1 in 1 and 2937 cm –1 in 2 is due the CH 2 stretching mode. A comparison with copper 1,2‐ethylenediphosphonate shows that the band at 1413 cm –1 ( 1 ) and 1426 cm –1 ( 2 ) is caused by the CH 2 bending mode, whereas the bands at 1543 and 1392 cm –1 ( 1 ) and at 1558 and 1393 cm –1 ( 2 ) represent the asymmetric (ν as ) and symmetric (ν s ) vibrations of the carboxylate group, respectively. The carboxylate group coordinates Cu 2+ in a monodentate manner (Figure and Figure ) and therefore a difference between ν as and ν s of ≥ 200 cm –1 should be expected .…”

“…Using bifunctional organophosphonates, e.g. diphosphonate or phosphonocarboxylate units as ligands, various structural motives can be made possible . Zinc 5‐phosphonobenzene‐1,3‐dicarboxylate can be used as catalyst in Friedel‐Crafts benzylation reactions and cobalt uranyl phosphonoacetate shows selective CO 2 uptake .…”

Synthesis, Crystal Structure and Characterization of Two Novel One- and Two-Dimensionally Polymeric Copper(II) Phosphonoacetates

“…The weak band at 2921 cm −1 in 1 and 2937 cm −1 in 2 is due the CH2 stretching mode. A comparison with copper 1,2ethylenediphosphonate [7] shows that the band at 1413 cm −1 (1) and 1426 cm −1 (2) is caused by the CH2 bending mode, whereas the bands at 1543 and 1392 cm −1 (1) and at 1558 and 1393 cm −1 (2) represent the asymmetric (νas) and symmetric (νs) vibrations of the carboxylate group, respectively. The carboxylate group coordinates Cu 2+ in a monodentate manner (Figure 3 and 7) and therefore a difference between νas and νs of ≥ 200 cm −1 should be expected.…”

Unusual adsorption-induced phase transitions in a pillared-layered copper ethylenediphosphonate with ultrasmall channels

“…The crystal structure of Cu-EtP (Cambridge Structural Database refcode UXUPEK) 46 is constituted of layers built from the connection of Cu II ions and phosphonate groups, pillared by the aliphatic chain of the linker (Fig. 1a and Fig.…”

“…13 500 and 10 000 cm À1 are observed, in agreement with previous report. 46 According to crystal field theory, and as already detailed in ref. 46 S50, ESI †).…”