II. EL HÉROE DE LOS SUBURBIOS
2.3. El antihéroe en Plata quemada
Phosphonate materials have been formed from numerous /7-block elements. The phosphonates formed from the group 15 elements include the antimony methylene diphosphonate; Sb2 0(0 3PCH2?0 3).^^ This material is composed o f a three-dimensional network of (p-trigonal bipyramidal [Sb0 4] units and tetrahedral [(CH2)P0 3] units, incorporating 9 membered Sb and P rings forming narrow structural channels. The use of ethylene and propylenediphosphonic acids result in two structurally similar materials Sb[0 3P(CH2)2P0 2(0H)] and Sb[0 3P(CH2)3P0 2(0 H)].*’ The bismuth carboxy- phosphonate material, Bi(0 3PC2H4C0 2).H2 0 has been reported in addition to the cluster, [(B u P 0 3 )-P -t]io [(B u P 0 3 H )-P -t]2 B i,4 0 ,o .3 (C 6 H 6 ).4 (H 2 0 )].® ‘’ ”
The phosphonate chemistry o f group 14 elements has recently developed a significant structural variety with the publication o f new tin compounds. The one dimensional structures [Sn(H0 3PCH2P0 3H)]-H2 0,^^ and Sn2(0 3PCH3)(C204),^^ two dimensional layered structures; Sn(0 3PCH2CH3),^'* and [Sn(0 3PC6H5)],^^ and a three dimensional framework tin material; Sn2[0 3PC(0H)(CH3)P0 3].^^ The materials typically exhibit truncated square pyramidal centred tin polyhedra by virtue o f the directional influence of the Sn(II) lone pair of electrons. As previously discussed, Pb(H0 3PC6H5)2
forms a structure analogous to Ba(H0 3PC6H5)2 layered structure with 8 coordinate metal
centres.^^
Research interest in phosphonate chemistry of group 13 elements, particularly aluminium, has exploded after the synthesis and characterisation of the AlMePO-a and AlMePO-p materials,^^’^^ with compositions Al2(0 3PCH3)3.n(H2 0), where n = 0-1.5 for the a- phase and « = 1 for the p- phase. Both compounds were prepared hydrothermally from pseudoboehmite A1(0H3) and methylphosphonic acid treated for 48 hours at 220 °C
for the a- phase and 160 °C for the P- phase. The a- phase consists o f imidimensional chanels which are completely lined by methylene groups. The inorganic framework which forms the channels is made up of 18-membered rings, composed of alternating
tetrahedral CPO3 and octahedral AlOg polyhedra. Additional 6-membered rings also exist
between the channels although their size is restricted by a lining of organic groups. The 18-membered ring channels have an effective diameter (considering the restriction of channel diameter by the organic lining) of 5.8 Â, however the a- phase is able to adsorb
2,2-dimethylpropane, which has a kinetic diameter of 6 .2 Â, demonstrating the flexibility of the methyl groups lining the channel wall. The p- phase possesses a structure similar to that for the a-, it is composed of identical 18-membered organically lined channels,
however these channels are not linked by smaller 6-membered channels. The structure of
AlMePO-p is shown in Figure 2.10. It also adsorbs 2,2-dimethylpropane. The a- and P- phases were characterised by adsorption techniques.^^ Both materials show similar properties, both are stable to heating at 500 C (at temperature in excess of 500 °C, the p- phase transforms into the a- phase), however the a- phase shows no adsorption of water whereas the p- phase shows an adsorption into the channels at P/Po ~ 0.7. Other, layered
aluminium phosphonates have been synthesised. AlMePO-Ç has composition
A1(0 H)(0 3PCH3)*H2 0 and a layered structure topologically identical to
V0 (0 3PC6H5)'H2 0 with octahedral AlOe units.^^ Al2(CH3P0 3)3, denoted ALMePG-y, is a layered material composed of aluminium atoms in tetrahedral and trigonal bipyramedal configurations.^®® Al3(CH3P0 3)2'0 '(0 H)3 is formed hydrothermally and has a stmcture with methyl lined aluminophosphonate layers with the aluminium atoms in octahedral and distorted trigonal bipyramidal structures.'®* Li2Al3(H0 3PCH3)2(0 3PCH3)4Ch7(H2 0) is synthesised using a melt method with a Li/Al layered double hydroxide mixed with molten methylphosphonic acid. The material has a layered structure composed of AlOe
Chapter 2: Introduction to M etal P hosp h onate M aterials
octahedra and C P O3 tetrahedra, Li^ ions are found within the layers and Cl ions the
interlayer r e g i o n . A similar synthetic method resulted in the formation o f the layered
A1(03PCH3)(H03PCH3) H2O, composed of aluminium centered o c ta h e d ra ,A ro m a tic
groups have been incorporated into aluminium phosphonates including the
phenylphosphonates,'^"^’'^^ and benzylphosphonates.’^ ’'^^’'^^ Aluminium phosphonates
have also been synthesised through intercalation of phenylphosphonates into known
aluminium inorganic phases, including layered double hydroxides and bayerite.'^^'^^^
Other phosphonates synthesised with functionality incorporated include the
carboxymethylphophonate, A1(03PCH2C02)'3(H20),''^ an aminopropylphosphonate,"’
and an aluminium nitrilophosphonate.112
The synthesis of new aluminium phosphonate phases was followed by reports of the synthesis of new gallium phases. The gallium equivalent of the layered, AlMePO-Ç, was synthesised,^^ as well as a series of layered gallium methylphosphonates, Ga(0H)(0 3PCH3)-xH2 0 (where % = 0 and 1).*^^ In addition the layered gallium methylphosphonate, Ga3(0 H)3F3(MeP0 3)2H2N(CH2)3NH3, was synthesized in the
presence of diaminopropane.*^*^ The three dimensional gallium diphosphonates,
Ga4(0 3PC2H4P03)3 and Ga2(0 H)2(0 3PC2H4P0 3) were recently reported. Both materials consist o f inorganic layers pillared by ethylenediphosphonate moieties the former is
composed of gallium in tetrahedral, Ga0 4, and trigonal bipyramidal, GaOs,
environments, the latter adopts an identical layer structure to Ga(0 H)(0 3PCH3) with gallium in an octahedral coordination.’’^ Other, functionalised, gallium phosphonates
include the carboxyethylphosphonates, Ga(0 H)(0 3PC2H4C0 2H) H2O and
Ga3(0 H)3(0 3PC2H4C0 2)2'2H2 0,” ^ and a range o f gallium
phenylphosphonates. ^ ^5J13, n 7, u s ^_block phosphonates include the paucity of
phosphonates reported for indium. These include the layered phenyl and
benzylphosphonates In(0 3PC6H5)(H0 3PC6H5) H2O’ and
In(0 3PCH2C6H5)(H0 3PCH2C6H5)*H2 0 and the layered indium methylphosphonate I n 2 ( 0 3 P C H 3 ) 3 - 2 H 2 0 . ” ^
Chapter 2: Introduction to Metal Phosphonate Materials
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