WO2016205405A1 - Polymère de coordination - Google Patents

Polymère de coordination Download PDF

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WO2016205405A1
WO2016205405A1 PCT/US2016/037679 US2016037679W WO2016205405A1 WO 2016205405 A1 WO2016205405 A1 WO 2016205405A1 US 2016037679 W US2016037679 W US 2016037679W WO 2016205405 A1 WO2016205405 A1 WO 2016205405A1
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coordination polymer
cyclic
dicyano
ligand
oligomeric complex
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Philip Boudjouk
Ryan SCHWIDERSKI
Kenneth Anderson
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North Dakota State University Research Foundation
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North Dakota State University Research Foundation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass

Definitions

  • the present application provides a new class of silicon-based coordination polymers.
  • the silicon-based coordination polymers may have potential as supramolecular assembly templating agents and could prove useful in a number of fields, including heterogeneous catalysis, reactive networks for production of silicon-based macromolecular structures, non-linear optical activity, porous materials for gas and ion storage, and photoluminescent materials.
  • the present application provides the synthesis of Lewis acid-base complexes of organopolycyanide ligands, e.g., organodicyanide ligands such as terephthalonitriles (1,4- dicyanobenzenes), and corresponding substituted analogues, with cyclic silane moieties to produce coordination polymers.
  • organopolycyanide ligands e.g., organodicyanide ligands such as terephthalonitriles (1,4- dicyanobenzenes), and corresponding substituted analogues
  • the present complexes provide examples of coordination polymers utilizing a silicon-based Lewis acid.
  • the Lewis acid-base complexes may include organodicyanide ligands complexed with cyclic perhalosilane moieties (such as Si 6 Cl i2 moieties) to produce 1-dimensional (i.e., linear) coordination polymers.
  • the organopolycyanide ligands may include
  • the application provides an oligomeric complex or a coordination polymer which includes at least three cyano functional ligands and at least two cyclic silanes (e.g., cyclic perhalosilanes) structurally incorporated with the ligands.
  • At least one of the three ligands is an organopolycyanide, such as a polycyano- substituted aromatic, aliphatic or
  • the coordination polymer includes a much larger number of ligands and cyclic perhalosilanes arranged in alternating placement in a 1 -dimensional array (e.g., long chains of alternating terephthalonitrile and Si 6 Cl 12 molecules in a one-to-one ratio).
  • the coordination polymer may have a unit structure, which includes an
  • organodicyanide ligand and the cyclic perhalosilane may have a unit structure, which includes a terephthalonitrile ligand and a cyclic perhalohexasilane or a cyclic perhalopentasilane.
  • the coordination polymer may include polycyano ligands which contain three or more cyano groups.
  • the cyclic silane commonly includes a 5-, 6- and/or 7-membered silane ring where the silicon atoms are substituted with halogen, alkoxy and/or cyano substituents.
  • the cyclic silane is a cyclic perhalosilane, e.g., where the silicon atoms are substituted with chloro-, bromo- or iodo- substituents.
  • all of the silicon atoms in a cyclic perhalosilane may be substituted with the same halogen substituent, e.g., dodecachlorocyclohexasilane or dodecabromocyclohexasilane.
  • the cyclic silane includes one or more cyclic
  • the cyclic perhalosilane may be a dodecahalocyclohexasilane or a decahalocyclopentasilane.
  • suitable dodecahalocyclohexasilanes include dodecachlorocyclohexasilane and dodecabromocyclohexasilane.
  • suitable decahalocyclopentasilanes include decachlorocyclopentasilane and
  • the organodicyanide may be a dicyano substituted aromatic compound, such as a dicyanobenzene (e.g., a terephthalonitrile) or dicyanonaphthalene (e.g., a 1,4-dicyano- naphthalene).
  • the cyano ligands may be optionally substituted with other substituents so long as the substituents do not interfere with the ability of the cyano group(s) to coordinate with a cyclic silane.
  • the organodicyanide ligand may be 1,4- dicyanobenzene ("terephthalonitrile"), optionally substituted with one or more chloro, fluoro and/or methyl substituents, e.g., l,4-dicyano-2,3,5,6-tetrafluorobenzene, 1,4-dicyano- 2,3,5,6-tetrachlorobenzene and/or l,4-dicyano-2,3,5,6-tetramethylbenzene.
  • terephthalonitrile 1,4- dicyanobenzene
  • substituents e.g., l,4-dicyano-2,3,5,6-tetrafluorobenzene, 1,4-dicyano- 2,3,5,6-tetrachlorobenzene and/or l,4-dicyano-2,3,5,6-tetramethylbenzene.
  • organodicyanide ligands include 1,4-dicyano cyclohexane, 1,2-dicyanoethane 1,3- dicyanopropane, 1,3-dicyano adamantane and the like.
  • organopolycyanide ligands include tricyano-substituted ligands (e.g., 1,3,5-tricyanobenzene) and/or tetracyano- substituted ligands (e.g., tetracyanomethane, tetracyanosilane, 1,2,3,4- tetracyanocyclobutane, 1,3,5,7-tetracyano adamantane and/or tetra-(p-cyanophenyl)-silane).
  • tricyano-substituted ligands e.g., 1,3,5-tricyanobenzene
  • tetracyano- substituted ligands e.g., tetracyanomethane, tetracyanosilane, 1,2,3,4- tetracyanocyclobutane, 1,3,5,7-tetracyano adamantane and/or tetra-(p-cyanoph
  • a method of producing a crystalline solid which includes a plurality of the present coordination polymers is also provided.
  • the method may include mixing a first solution of the cyclic perhalosilane dissolved in a solvent and a second solution of the organodicyanide dissolved in the solvent.
  • the method may also include heating the first and second solutions before the mixing step.
  • Figure 1 depicts a thermal ellipsoid plot of the "inverted sandwich" type structure of a hypercoordinated silicon complex between a Si 6 Cl 12 ring and two 1,4-dicyanobenzenes (CP1) at the 50% probability level (hydrogen atoms not shown for clarity purposes).
  • Figure 2 depicts the intermolecular 0 ⁇ 0 contacts that are responsible for the crystal packing in the hypercoordinated silicon complex CP1 (ligands not shown for clarity purposes).
  • Figure 3 depicts the crystal packing in crystals of the hypercoordinated silicon complex CP1 showing the view along the b-axis.
  • Figure 4 depicts a view of the ligand— Si 6 Cli 2 interactions highlighting the angle of tilt the ligands exhibit in reference to the calculated plane of the Si 6 Cli 2 ring in crystal packing for the hypercoordinated silicon complexes CP1, CP2 and CP3.
  • Figure 5 depicts the crystal packing in the hypercoordinated silicon complex CP1 showing the view along the a-axis.
  • the present materials may be produced by methods as exemplified by the synthesis of Lewis acid-base complexes of terephthalonitriles (1,4-dicyanobenzenes) and corresponding substituted analogues, with Si 6 Cl 12 moieties to produce 1-dimensional coordination polymers, as illustrated in Scheme 1 below.
  • Scheme 1 illustrates the synthesis of terephthalonitrile* Si 6 Cli 2 coordination polymers from the self-assembly of the Lewis acid, perchlorocyclohexasilane, and corresponding terephthalonitrile Lewis base.
  • a crystalline solid comprising a plurality of the present coordination polymers.
  • the crystalline solid may have a crystal structure where the organodicyanide ligand (e.g., terephthalonitrile) is aligned in a substantially
  • the orientation may be slightly tilted from perpendicular.
  • the organodicyanide ligand is 1,4-dicyanobenzene and the cyclic perhalosilane is dodecachlorocyclohexasilane; the terephthalonitrile may be aligned at an angle of about 83 degrees to the plane of the cyclic perhalosilane ring.
  • the organodicyanide ligand is l,4-dicyano-2,3,5,6-tetrafluorobenzene and the cyclic
  • the terephthalonitrile may be aligned at an angle of about 75 degrees to the plane of the cyclic perhalosilane ring.
  • the organodicyanide ligand is l,4-dicyano-2,3,5,6-tetrachlorobenzene or l,4-dicyano-2,3,5,6- tetramethylbenzene and the cyclic perhalosilane is dodecachlorocyclohexasilane
  • the terephthalonitrile may be aligned at an angle of about 90 degrees to the plane of the cyclic perhalosilane ring.
  • a method of producing a crystalline solid which includes a plurality of the present coordination polymers is also provided.
  • the method may include mixing a first solution of the cyclic perhalosilane dissolved in a solvent and a second solution of the organodicyanide dissolved in the solvent.
  • the method may also include heating the first and second solutions ⁇ e.g., to about 70 - 80 °C ⁇ before the mixing step.
  • the a crystalline solid may also be produced by a method which includes forming a first solution of a cyclic perhalosilane dissolved in a halocarbon solvent and a second solution of an organodicyanide dissolved in a halocarbon solvent; and mixing the first and second solutions.
  • the a crystalline solid may also be produced by a method which includes heating a first solution of a cyclic perhalosilane dissolved in a halocarbon solvent; heating a second solution of an organodicyanide dissolved in the halocarbon solvent.
  • the first and second solutions are typically only mixed sufficiently to ensure that a homogenous solution is formed.
  • the homogenous solution is then commonly allowed to stand unmixed at ambient temperature (-25 - 30 °C) until crystals of the coordination polymer are formed.
  • Coordination polymers CP1-CP4 were synthesized using the reaction conditions that involved dissolving both the Si 6 Cli 2 and the terephthalonitriles in 1,2-dichloroethane (1,2-DCE) and heating each mixture to near boiling (see Scheme 1 above). Once heated, the terephthalonitrile (l-4)/l,2-DCE solution was added to the Si 6 Cli 2 /l,2-DCE solution and stirred just long enough to ensure a homogenous solution.
  • Unpolarized Raman spectra were collected in a spectral range of 100-3400 cm-1 at a resolution of ⁇ 1 cm-1 with a LabRAM Aramis Horiba Jobin Yvon confocal Raman microscope equipped with a CCD using a 785 nm coherent excitation source.
  • X-ray Crystallography X-ray quality crystals of CP1 precipitated out of hot 1,2- dichloroethane after approximately 1 minute upon addition of terephthalonitrile. Crystals of CP2 and CP3 were generated by slow precipitation out of hot 1,2-dichloroethane, which took between 2 hours and 12 hours, respectively.
  • the frames were integrated with the Bruker SAINT software package.
  • the unit cell was determined and refines by least-squares upon the refinement of XYZ-centroids of reflections about 20s(I).
  • the structure was refined using the Bruker SHELXTL (Version 5.1) software package.
  • the crystal data, data collection parameters, and refinement statistics are listed below in Table 1.
  • the Raman spectra of these complexes also support the formation of coordination polymers with the appearance of a few distinct features.
  • the Raman spectra of the polycrystalline complexes were obtained with 785 nm laser excitation. All the coordination polymers, CP1-CP4, exhibit characteristic v(Si-Si) and v(Si-Cl) vibrations at approximately 257 cm-1 and 583 cm-1 respectively.
  • the Si 6 Cli 2 •terephthalo-nitrile complexes also exhibited red shifts in some of the frequencies that correspond to the vibrations of the nitrile and benzene ring moieties of the terephthalonitrile ligands (Table 2).
  • Table 2 shows the Raman and IR shifts of the terephthalonitriles and corresponding Si6Cli 2 *terephthalontrile complexes.
  • the complexes show red shifts in the v(C ⁇ N) and v(C-C) vibrations of approximately 8-10 cm-1 and 9-14 cm-1, respectively.
  • the terephthalonitrile ligands behave similarly in the solid state as previously observed for neutral benzonitrile ligand coordination with perhalogenated cyclohexasilanes.
  • the lone pair of electrons on the nitrile appears to be shared between the six silicon atoms of the Si 6 Cli 2 ring (see Figure 1). This interaction seems to be fairly consistent among benzonitrile type ligands as the compounds synthesized exhibit CN— Si coordination distances between 3.000 and 3.524 A, depending on the benzonitrile employed (see Table 3).
  • Table 3 shows a comparison of crystallographic features of coordination polymers CP1-CP3 to the structurally similar inverse sandwich type structure of Si6Bri 2 ?-tolunitrile. Values given in parentheses indicate distance from Si 6 Cl 12 calculated centroid to the nitrogen of the C ⁇ N group in A.
  • Si 6 Cli 2 and various substituted terephthalonitriles (1-4) A trend observed with Si 6 Cli 2 and various substituted terephthalonitriles (1-4) is that with increasing bulkiness of groups at the C3 and C4 positions, an increase in the CN— Si distance is also observed. It has also been observed that the planarity of the Si 6 Cli 2 ring is affected by the CN— Si coordination distance. The Si-Si torsion angles of the ring get larger with the increase in CN— Si distance that is correlated with the steric bulk of the substituents on the terephthalonitriles. The Si-Si torsion angles increase from -2.5° in CPl, where hydrogens are the substituents and up to -5.50° in CP3, where terephthalonitrile is substituted with chlorine substituents.
  • the crystals of these coordination polymers arise from two main interactions, which are the Lewis acid-Lewis base coordinations and the chlorine-chlorine halogen bonds formed from close proximity Si 6 Cli2 rings.
  • the ligand-Si 6 Cli2 interactions drive the formation of linear, 1 -dimensional structures that cause the formation of needle-like crystals to be favored, but the close packing nature of the crystals is driven by the halogen bonding contacts of neighboring Si 6 Cli 2 rings.
  • These chlorine-chlorine contacts are observed in the crystals of all of the coordination polymers (CP1-CP4) and all follow similar close contact trends asdisplayed in Figure 2.
  • the central ring shares chlorine contacts with eight other rings, four above and four below the plane of the central ring. Four of the neighboring rings share a greater number of chlorine-chlorine contacts and are held tighter to the central ring. Whereas, the other four rings exhibit fewer chlorine-chlorine contacts and are further away. This feature is illustrated in Figure 3.
  • each Si 6 Cl 12 ring has eight other Si 6 Cl 12 rings in contact (only four can be seen as the rings below are masked by the rings above).
  • the blue lines shown in Figure 3 represent contacts from chlorines on the rear Si 6 Cli 2 rings and red lines the front rings.
  • two flanking rings share chlorine-chlorine contacts with the central ring in a manner that aligns the neighboring chlorines directing in-line with the chlorines on the central ring, while the other two rings have chlorines that are out a ways from the central ring chlorines.
  • This crystal packing feature is shared in all of the coordination polymers derived from these materials and leads to layered ordering of the Si 6 Cl 12 rings throughout the material.
  • Another important aspect of these materials is the orientation of the ligand, as this also contributes to the order of the Si 6 Cli 2 rings in the solid-state.
  • the substituents on the terephthalonitrile have a large effect on the angle the ligand sits in the Si 6 Cli 2 cavity. It appears the larger substituents caused a greater ligand angle as CP2 sits at an angle of -75° in the cavity and CP1 sits at an angle of -83° ( Figure 1.1-4).
  • the ligand in CP3 sits completely perpendicular to the Si 6 Cli 2 ring even though the chlorines are larger than the hydrogen and fluorine substituents of CP1 and CP2.
  • Figure 4 shows a view of the ligand— Si 6 Cli 2 interactions highlighting the angle of tilt the ligands experience in reference to the calculated plane of the Si 6 Cl 12 ring in crystal packing with a) terephthalonitrile at 83.46° in CP1; b) tetrafluoroterephthalonitrile at 74.96° in CP2; and c) tetrachloroterephthalonitrile at 90.00° in CP3.
  • the effect of these interactions on the solid-state packing properties of these materials is the appearance of an apparent handedness in alternating coordination polymer planes when the ligand does not sit perpendicular to the Si 6 Cli 2 ring in the solid-state ( Figure 5).
  • one plane of CP1 has Si 6 Cl 12 rings that lean to the right, whereas the next plane has rings that lean to the left (i.e., in the opposite direction to the adjacent plane).
  • This pattern of alternating right-leaning and left-leaning Si 6 Cli 2 rings is continued throughout the crystal and is accentuated in materials where the ligand tilts to a greater degree in the Si 6 Cli 2 cavity, i.e. CP2
  • polycyanide ligands include cyanogen, tetracyanomethane, tetracyanosilane, dicyanoacetylene, polycyanosubstituted cycloaliphatic compounds, such as tetracyanocyclobutane, tricyanocyclopropane and dicyano bicyclo[2.2.2]cycloaliphatic compounds, cyano substituted aromatic hydrocarbons, such as cyano substituted benzenes, cyano substituted anthracenes, cyano substituted biphenyls and cyanophenyl substituted anthracenes, and dicyanoalkylenes having a backbone methylene substituted by a heteroatom (e.g., -0-, -S- or -N(R)-).
  • a heteroatom e.g., -0-, -S- or -N(R)-
  • One embodiment provides an oligomeric complex or a coordination polymer comprising: at least three ligands and at least two cyclic perhalosilanes structurally incorporated with the ligands, wherein at least one of the at least three ligands is an organopolycyanide.
  • the coordination polymer may have a unit structure, which includes an organodicyanide ligand and the cyclic perhalosilane, e.g., coordination polymer may have a unit structure, which includes a terephthalonitrile ligand and a cyclic perhalosilane.
  • the cyclic perhalosilane may be a compound which includes 4 - 7 silicon atoms, such as a cyclic perhalohexasilane or a cyclic perhalopentasilane.
  • the cyclic perhalosilane may be a dodecahalocyclohexasilane or a
  • Examples of suitable dodecahalocyclohexasilanes include dodecachlorocyclohexasilane and dodecabromocyclohexasilane.
  • Examples of suitable decahalocyclopentasilanes include decachlorocyclopentasilane and
  • the polycyanide ligand may include cyano substituted aromatic compound, a cyano substituted aliphatic compound and/or a cyano substituted cycloaliphatic compound.
  • the organopolycyanide ligand typically includes two (2) or three (3) cyano groups.
  • the organopolycyanide may include 1,2-dicyanoethane, fumaronitrile, bis-(2- cyanoethyl) ether, 1,6-dicyanohexane, 1,3-dicyanopropane and/or 1,4-dicyanocyclohexane.
  • tetracyano-substituted ligands such as tetracyanomethane, tetracyanosilane, 1,2,3,4-tetracyanocyclobutane, 1,3,5,7-tetracyano adamantane and tetra- (p-cyanophenyl)-silane
  • tricyano-substituted ligands such as 1,3,5-tricyanobenzene, 1,3,5-tricyano adamantane and 1,2,3-tricyanocyclopropane.
  • the polycyanide ligand may include one or more dicyano aliphatic compounds, dicyano cycloaliphatic compounds and/or dicyano aromatic hydrocarbon compounds.
  • the polycyanide ligand may include a dicyano cycloaliphatic compound such as a dicyanocyclohexane, dicyanocyclopentane and/or dicyano bicycloaliphatic compound, optionally substituted with one or more halogen, alkyl and/or alkoxy substituents.
  • the dicyano bicycloaliphatic compound may be a dicyano bicyclo[2.2.2]hydrocarbon compound and/or dicyanonorbornane compound.
  • Suitable examples include 2,3 -dicyanonorbornane, 2,5-dicyanonorbornane, 2,6-dicyanonorbornane, 1,4-dicyano bicyclo[2.2.2]octane, l,4-dicyano-2,3,5,6-tetramethyl bicyclo[2.2.2]octane, l,4-dicyano-2,3,5,6-tetramethyl bicyclo[2.2.2]octa-2,5,7-triene.
  • the polycyanide ligand may include one or more dicyano aromatic hydrocarbon compounds, such as a dicyanobenzene, dicyanonaphthalene, dicyanoanthracene and/or dicyanobiphenyl, any of which may optionally be substituted with one or more substituents, e.g., halogen, alkyl and/or alkoxy substituents.
  • substituents e.g., halogen, alkyl and/or alkoxy substituents.
  • Suitable examples include 9,10-dicyanoanthracene, 1,4-dicyanoanthracene, 1,5-dicyanoanthracene, 1,4- dicyanonaphthalene, 1,5-dicyanonaphthalene and/or 4,4'-dicyanobiphenyl.
  • suitable dicyano aromatic hydrocarbon compounds include bis-(p-cyanophenyl)- substituted aromatic hydrocarbons.
  • the bis-(p-cyanophenyl)-substituted aromatic hydrocarbon may be 9, 10-bis-(p-cyanophenyl)-anthracene, l,4-bis-(p- cyanophenyl)-naphthalene and/or l,4-bis-(p-cyanophenyl)-benzene, where these
  • compounds may optionally be substituted with one or more substituents, e.g., halogen, alkyl and/or alkoxy substituents.
  • substituents e.g., halogen, alkyl and/or alkoxy substituents.
  • the polycyanide ligand may include one or more dicyano aliphatic compounds and/or related derivatives, e.g., dicyano aliphatic compounds represented by formula A:
  • NC-(CH 2 ) compassion-CN (A) wherein n is an integer from 1 to 30 and the alkylene chain may optionally have one or more of the methylene units replaced with a heteroatom (e.g., -0-, -S- or -N(R)-, where R is alkyl or aryl) and/or unsaturated bond.
  • Suitable examples include fumaronitrile, dicyanoacetylene, 1,3-dicyanopropane, 1,4-dicyanobutane , 1,6-dicyanohexane and 1,2- dicyanoethylene.
  • the organodicyanide may be an aromatic dicyano compound, such as a
  • the organodicyanide ligand may be 1,4-dicyanobenzene, 1,4-dicyano- 2,3,5,6-tetrafluorobenzene, 1,4-dicyano- 2,3,5,6-tetrachlorobenzene and/or 1,4-dicyano- 2,3,5,6-tetramethylbenzene.
  • suitable examples include bis-(p- cyanophenyl) substituted aromatic hydrocarbons, such as l,4-bis-(p-cyanophenyl)-benzene, and cyano substituted naphthalenes and anthracenes.
  • crystalline solid which includes a plurality of the present coordination polymers.
  • the crystalline solid may have a crystal structure in which the ligands are aligned in a substantially perpendicular orientation to the plane of an adjacent cyclic perhalosilane ring.
  • the ligand is 1,4-dicyanobenzene or 1,4-dicyano- 2,3,5,6-tetrafluorobenzene
  • the crystalline solid may have a crystal structure including alternating right-leaning and left-leaning layers of cyclic perhalosilane rings.
  • the major axis of the terephthalonitrile may be aligned at an angle of about 83 degrees to the plane of the cyclic perhalosilane ring.
  • the organodicyanide ligand is l,4-dicyano-2,3,5,6-tetrafluorobenzene and the cyclic
  • the major axis of the terephthalonitrile may be aligned at an angle of about 75 degrees to the plane of the cyclic perhalosilane ring.
  • the organodicyanide ligand is l,4-dicyano-2,3,5,6-tetrachlorobenzene or 1,4-dicyano- 2,3,5,6-tetramethylbenzene and the cyclic perhalosilane is dodecachlorocyclohexasilane
  • the major axis of the terephthalonitrile is typically aligned at an angle of about 90 degrees to the plane of the cyclic perhalosilane ring.
  • the crystalline solid has a crystal structure including a layered ordering of cyclic perhalosilane rings.
  • the cyclic perhalosilane is a cyclic dodecahalocyclohexasilane; and the crystalline solid has a crystal structure in which each cyclic perhalohexasilane has halogen bonding contacts with 8 adjacent
  • the oligomeric complex or coordination polymer includes a plurality of dodecachlorocyclohexasilane moieties and a plurality of linking ligands.
  • Each linking ligand is 1,4-dicyanobenzene and/or a substituted 1,4-dicyanobenzene.
  • linking ligand means a chemical species that can coordinate two or more dodecachlorocyclohexasilane moieties resulting in a predetermined separation and a defined framework that is produced. Examples include 1,4-dicyanobenzene and substituted 1,4- dicyanobenzenes.
  • the oligomeric complex or coordination polymer includes at least one dodecachlorocyclohexasilane moiety structurally incorporated between two ligands, wherein the two ligands are 1,4-dicyanobenzene and/or a substituted 1,4- dicyanobenzene.
  • the substituted 1,4-dicyanobenzene may be 1,4-dicyano- 2,3,5,6- tetrafluorobenzene, 1,4-dicyano- 2,3,5,6-tetrachlorobenzene or 1,4-dicyano- 2,3,5,6- tetramethy lb enzene .

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Abstract

Cette invention concerne des complexes oligomères à base de silicium et des polymères de coordination. Les complexes oligomères et les polymères de coordination contiennent au moins trois ligands cyano fonctionnels et au moins deux silanes cycliques (p. ex., perhalosilanes cycliques) structuralement incorporés aux ligands. Un procédé de formation desdits complexes oligomères et polymères de coordination et des solides cristallins comprenant une pluralité desdits polymères de coordination sont en outre décrits.
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