3D coordination polymers

Mir MH, Koh LL, Tan GK, Vittal JJ (2010) Single-crystal to single-crystal photochemical structural transformations of interpenetrated 3D coordination polymers by [2-1-2] cycloaddition reactions. Angew Chem Int Ed Engl 49 390-393... 

Unlike [Fe6Cl6(L14)6] (39a) (Sect. 7.1), the ferric wheels of [Fe6Cl6(L17)6] (39d) are not arranged in parallel but rather are three-dimensionally perpendicular (Fig. 16) [114-116], a well-known arrangement for 3D-coordination polymers (Sect. 9.2, Fig. 18). 

Reaction of tetrazolyl enole 45 with copper(II) acetate yields the 3D-coordination polymer [ CulL19)21 (46), the structure of which is unequivocally established by single-crystal X-ray diffraction. The formation of 46 is understandable if the enolate of 45 is considered as tridentate chelate ligand and if the intermediate formation of the coordinatively unsaturated self-complimentary copper(II) building block 47 is assumed. The monomers 47 are bidentate coordinating by the two CN donors, which leads to linking of monomers and to coordinative saturation at the copper(II) center of 47 with formation of three-dimensional 0 [Cu(L19)2] (46) (Scheme 17, Fig. 18) [163, 164],... 

In the 2D-, and 3D-coordination polymers discussed so far, a given monomer is surrounded by a total of four monomeric building blocks. Two of them are connected perpendicular to the axial position (Cu <— NC acceptor interaction), and two are connected equatorial (CN —> Cu donor interaction) to the central monomer. 

In contrast, when ethyl aminomethylene cyanoacetate of type 58 [H2(L23)] is reacted with copper(II) acetate, a one-dimensional stair-like rather than a 2D- or 3D-coordination polymer [CufL23)] (59) is generated. In 59, the monomers [Cu(L23)] (60) are not arranged perpendicularly as in the 2D-/3D-case, but parallel,... 

Reaction of a methanolic solution of copper(II) acetate and enantiomerically pure (/ )/(S)-methyl( )-4ethyl-2-oxazolidinylidene)cyanoacetate 64 leads to the coordinatively unsaturated CVsymmetric intermediates (R,Rj-65 and (S,S)-65, which are sterically shielded at one side by two ethyl groups. Therefore, in contrast to the 2D- and 3D-coordination polymers, coordination of (R,R)/(S,S)-65 with only one cyano donor is possible, resulting in the formation of polymers (/>)-oc1[Cu(Li )2] (P-66) and (M)-J[Cu(L5)2] (M)-66) (Scheme 24) ([166, 169, 170] for other chiral lD-coordination polymers of our group, see [171, 172]). The X-ray crystal structure analysis of polymer (P)-66 clearly proves a well-ordered infinite onedimensional architecture. The central copper atoms in (P)- [Cu(L )2] CP-66) are almost tetragonal-pyramidally coordinated, and in contrast to the 2D- and... 

Figure 9.6 Temperature dependence of xm for [NdFe] 1 (o) and [NdCo] 2 ( ) at 10 kOe. Inset is the curve of xmF versus T at 500 Oe [68]. (Reprinted with permission from B. Ma, et al., Cyano-bridged 4f-3d coordination polymers with a unique two-dimensional topological architecture and unusual magnetic behavior, ChemieInternational Edition, 2001,40,434-437 (Figure3). WUey-VCH...

Kou, H., Zhou, B., and Wang, R. (2003) Heterotrimetallic 4f—3d coordination polymers synthesis, crystal structure, and magnetic properties. Inorganic Chemistry, 42, 7658—7665. 

Fe HB(tz)3 2]C104-2MeCN, octahedral, has been employed as a molecular building block. The noninterpenetrating 3D coordination polymer framework of [Fe HB(tz)3 2][Rh2(OAc)4]3-xS (S = solvent) has been prepared and characterized by single-crystal X-ray structure analysis.244... 

Note that a number of supramolecular materials of practical importance today, such as zeolite inclusion compounds, microporous silicas, and most 3D coordination polymers, do not satisfy one or more of the listed conditions. 

For all of the samples studied and for particle sizes down to the lowest studied, 150 nm, very similarly shaped SCO transition curves were observed and taken to imply that no significant size effect influenced the SCO process, at least in these particular nano-objects. Nanocrystals of the 3D coordination polymer [Fe(prazine)Pt(CN)4], which displays SCO properties in the bulk, also preserve the same magnetic, structural and optical bistability for particle sizes on the order of 50 nm. Recent evidence suggests however that this may not always be the case, as in the example of the 2D coordination polymer [Fe(3-fluoropyridine)2M(CN)4] where the bulk SCO properties were shown to be very markedly influenced by the nanoparticle dimen-sions. Detailed discussion of this topic falls outside the scope of this review but we refer to it here because it is an aspect of spin crossover studies that bears fundamentally" " on the practical application in device teehnology of nano-dimensioned SCO materials, which continue to display hysteretie behaviour at such dimensions. 

R. Robson 3D coordination polymers based on rod-like linkers... 

The catecholate functionality of CTC should make it a more effective metal binder than is CTV, although there are few known examples. A discrete trinuclear chelate complex of deprotonated CTC with Pt(II) has been reported. The manganese hydroxide-linked MeLa tetrahedra of the type discussed in Section 4.1.2 link into a complicated 3D coordination polymer through bridging oxides and sandwich-type interactions to additional Cs + cations that occur between (MnOH)6L4 tetrahedra. ... 

As in previous cases, this chapter only presents the simplest examples in order to illustrate the principles used for the assembly of 3D coordination polymers. For a more detailed discussion of the possible structural nets the reader is recommended to read Ref. 1. Two of the simplest 3D nets are the diamondoid and octahedral structurals and it is... 

In fact, the early developed Prussian blue, octahedral mixed-valance iron metal ions bridged by cyanide with the general formula Fe4[Fe(CN)6]3 xH20, its first single-crystal X-ray diffraction characterization was conducted by Ludi and coworkers, confirmed the potential to construct 3D coordination polymers through control of metal coordination and assisted metal-ligand assembly. 

Figure 3 Hoskins and Robson s first report of a 3D coordination polymer based on diamondlike net. The tetrafluoroborate counterions were highly disordered and not localized in the X-ray crystal structure. ...

Consequently, the construction of spin transition ID, 2D or 3D coordination polymers has attracted attention in recent years, and may form the base in new devices for memory, display and other magneto-optical applications [71-79],... 

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