Engineering 2D→2D parallel interpenetration using long alkoxy-chain substituents

Vujovic, Srboljub; Constable, Edwin C.; Housecroft, Catherine E.; Morris, Collin D.; Neuburger, Markus; Prescimone, Alessandro

doi:10.1016/j.poly.2015.03.010

Cited by 22 publications

(38 citation statements)

References 38 publications

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“…We have demonstrated that the length of such tails can have a significant impact on the outcome of assembly processes [13,14,15]. Single crystals grown by layering a MeOH solution of Co(NCS) 2 over a CHCl 3 solution of 8 were not of X-ray quality.…”

Section: Resultsmentioning

confidence: 99%

“…Rotation about the C–spacer bonds permits the node to have limiting planar or approximately tetrahedral geometries, and the directionality of the assembly can be modified by switching from 4,2’:6’,4”-tpy to 3,2’:6’,3”-tpy domains. We have recently employed such ditopic ligands in which the spacer (Scheme 1c) is a 1,4-C 6 H 4 ring to assemble parallel interpenetrating 2D→2D sheets [13,14,15] and 3D-metal-organic frameworks (MOFs) [15,16]. Going to a ferrocen-1,1’-yl spacer introduces rotational freedom and, in [{Zn 2 ( 1 )Cl 4 }∙3CHCl 3 ] n where 1 = 1,1’-bis(4,2’:6’,4”-terpyridin-4’-yl)ferrocene (Scheme 2), the ligand adopts a cisoid-conformation, leading to a double-stranded 1D-polymer chain [17].…”

Section: Introductionmentioning

confidence: 99%

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4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

et al. 2017

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A comparative investigation of the coordination assemblies formed between Co(NCS)2 and two monotopic 4,2’:6’,4’’-terpyridine (4,2’:6’,4”-tpy) ligands or two related ditopic ligands is reported. Crystals were grown by layering MeOH solutions of Co(NCS)2 over a CHCl3 or 1,2-C6H4Cl2 solution of the respective ligand at room temperature. With 4’-(2-methylpyrimidin-5-yl)-4,2’:6’,4”-terpyridine (6), the 1D-coordination polymer {[Co2(NCS)4(MeOH)4(6)2]∙2MeOH∙8H2O}n assembles with 6 coordinating only through the outer N-donors of the 4,2’:6’,4”-tpy unit; coordination by the MeOH solvent blocks two cobalt coordination sites preventing propagation in a higher-dimensional network. A combination of Co(NCS)2 and 1-(4,2‘:6’,4”-terpyridin-4’-yl)ferrocene (7) leads to {[Co(NCS)2(7)2]∙4CHCl3}n which contains a (4,4) net; the 2D-sheets associate through π-stacking interactions between ferrocenyl and pyridyl units. A 3D-framework is achieved through use of the ditopic ligand 1,4-bis(npropoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene (8) which acts as a 4-connecting node in {[Co(NCS)2(8)2]∙2C6H4Cl2}n; the combination of metal and ligand planar 4-connecting nodes results in a {65.8} cds net. For a comparison with the coordinating abilities of the previously reported 1,4-bis(noctoxy)-2,5-bis(4,2’:6’,4”-terpyridin-4’-yl)benzene (3), a more flexible analogue 9 was prepared. {[Co(NCS)2(9)]∙2CHCl3}n contains a (4,4) net defined by both metal and ligand planar 4-connecting nodes. The noctoxy tails of 9 protrude from each side of the (4,4) net and thread through adjacent sheets; the arene-attached noctoxy chains associate through a combination of van der Waals and C–H...π interactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

et al. 2017

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“…going from n octoxy to methoxy functionalization) causes the profile of the corrugated sheet to change. 14 (5) . 2MeOH] n , the alkoxy chain lies over two pyridine rings of a 4,2':6',4''-tpy unit (Fig.…”

Section: Alkoxy Chains: 2d→ → → →2d Parallel Interpenetrated Sheetsmentioning

confidence: 99%

“…In contrast, combining 2 (Scheme 3) with ZnCl 2 or ZnBr 2 leads to 2D-sheets in which the ligands are the unique nodes. 13,14 While the (4,4) (2)}] n , and are threaded within the interpenetrated sheets. We have previously suggested that the long chains may assist in directing the assembly process.…”

Section: Introductionmentioning

confidence: 99%

What a difference a tail makes: 2D → 2D parallel interpenetration of sheets to interpenetrated nbo networks using ditopic-4,2′:6′,4′′-terpyridine ligands

et al. 2017

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“…Formation of micelles, which aggregate to form cylindrical vesicles, is an alternate possibility (16). Constable, Housecroft et al (38)(39)(40)(41) recently studied the effects of alkylation (C 8 vs. Me) on gauge the effect of counterions and solvent on morphology with this system, 4 (Cl − ) was cast utilising a solvent mixture of MeCN/CHCl 3 (5/1). Disordered lamellae but no rods were observed (S10); however, the TEMs of 4 (Cl − ) cast from CHCl 3 /MeoH (2:1) are shown in Figures 9 and 10.…”

Section: Microscopymentioning

confidence: 99%

Amphiphilic [tpy-M^II-tpy] metallotriangles: synthesis, characterisation and hierarchical ordering

Ludlow

Saunders

Huang

et al. 2016

Supramolecular Chemistry

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Long chain (C 16 ) alkylated metallocycles are synthesised and characterised. Their ordered aggregation was studied via TEM to gauge to the effects of molecular topology, solvent, counterion and metal centre(s) on morphology and nanoscale structure. The results indicate that their amphiphilicity significantly enhanced their self-ordering characteristics relative to controls and enabled the formation of nanoscale structures. Similar ordering was observed for both labile and non-labile analogues with SAXD showing comparable d-spacing values, suggesting the presence of intramolecular π-π stacking. Effect of counterion and solvent was studied with the non-labile system. Nanotubular, ribbon, or sheet-like structures were afforded depending upon conditions. Downloaded by [University of Nebraska, Lincoln] at 13:16 18 May 2016 2 J. M. LuDLoW III ET AL.Nature provides examples of self-assembly of metal complexes into nanostructures, namely, the self-ordering of chlorophyll b (BChl) into rolls of light-adsorbing arrays by photosynthetic bacteria (18). BChl is a macrocyclic metal complex [porphyrin (Mg II )] with alkyl chains, ranging in size from C 16 to C 20 (24). Thus, BChl is amphiphilic possessing both a hydrophilic, ionic metal complex region and a hydrophobic chain. Synthetic amphiphiles including surfactants and amphiphilic block copolymers have also been used to create ordered structures (17) and the field of supra-amphiphiles has been pioneered by the Zhang group (25,26). Studies of hierarchical ordering of amphiphilic metallocycles are limited to those using pyridine (15), bipyridine ligands (27), phthalocyanine (28) and porphyrins (29). Investigation into self-ordering of [tpy-M IItpy]-based supramolecular structures using non-covalent intermolecular interactions has been generally focused on using ion pairing (9,10,14) to enhance intermolecular stacking. Previous studies looking into hierarchical ordering of [tpy-M II -tpy]-based amphiphiles (9, 14) only used non-labile complexes and did not use controls to gauge the effect of amphiphilicity in the observed ordering. This study includes such comparisons in order to provide a foundation for future investigations with [tpy-M II -tpy] systems and their hierarchial ordering into nanostructures (scheme 1). Given the limited information concerning self-ordering of amphiphilic, terpyridine-based metallosuprastructures, unanswered questions include (1) how does the introduction of hydrophobic/hydrophilic-type interactions impact ordering? (2) Does lability of the [tpy-M II -tpy] complex affect ordering? (3) Does counterion type affect ordering? (4) How does the solvent system affect ordering? To address these questions, we synthesise, characterise and evaluate self-ordering of a simple series of metallotriangles

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Engineering 2D→2D parallel interpenetration using long alkoxy-chain substituents

Abstract: The structural consequences of reducing the length of the alkoxy substituents on going from the ditopic ligand 1,4-bis(n-octoxy)-2,5-bis(4,2':6',4''-terpyridin-4'-yl)benzene (1) to 1,4-bis(methoxy)-2,5-bis(4,2':6',4''-terpyridin-4'-yl)benzene (2)

Cited by 22 publications

References 38 publications

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

What a difference a tail makes: 2D → 2D parallel interpenetration of sheets to interpenetrated nbo networks using ditopic-4,2′:6′,4′′-terpyridine ligands

Amphiphilic [tpy-M^II-tpy] metallotriangles: synthesis, characterisation and hierarchical ordering

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Engineering 2D→2D parallel interpenetration using long alkoxy-chain substituents

Abstract: The structural consequences of reducing the length of the alkoxy substituents on going from the ditopic ligand 1,4-bis(n-octoxy)-2,5-bis(4,2':6',4''-terpyridin-4'-yl)benzene (1) to 1,4-bis(methoxy)-2,5-bis(4,2':6',4''-terpyridin-4'-yl)benzene (2)

Cited by 22 publications

References 38 publications

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

4,2’:6’,4”- and 3,2’:6’,3”-Terpyridines: The Conflict between Well-Defined Vectorial Properties and Serendipity in the Assembly of 1D-, 2D- and 3D-Architectures

What a difference a tail makes: 2D → 2D parallel interpenetration of sheets to interpenetrated nbo networks using ditopic-4,2′:6′,4′′-terpyridine ligands

Amphiphilic [tpy-MII-tpy] metallotriangles: synthesis, characterisation and hierarchical ordering

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Amphiphilic [tpy-M^II-tpy] metallotriangles: synthesis, characterisation and hierarchical ordering