62 Porphyrin-Based Tectons in Molecular Tectonics

Bulach, Véronique; Hosseini, Mir Wais

doi:10.1142/9789814322386_0014

Cited by 7 publications

(7 citation statements)

References 99 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…9 Moreover, the possibility of appending the porphyrin backbone with peripheral interaction sites at specific positions (meso or β-pyrrolic) allows for implementing additional functionality. In line with the molecular tectonics approach, [10][11][12][13] porphyrin based tectons 14,15 have been largely used for the generation of a variety of 1-3D coordination networks 16,17 in the crystalline phase.…”

Section: Introductionmentioning

confidence: 99%

From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

Studener

Müller

Marets

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

The self-assembly of a metal-free porphyrin bearing two pyridyl coordinating sites and two pentyl chains at trans meso positions was investigated under ultrahigh vacuum on a Ag(111) surface by scanning tunneling microscopy (STM). The STM measurements revealed a well-ordered close-packed structure with a rhombic unit cell for coverages ≤1 monolayer with their molecular plane parallel to the surface. The growth direction of the molecular islands is aligned along the step edges, which are restructured due to molecule-substrate interactions. The shorter unit cell vector of the molecular superstructure follows the〈1-10〉direction of the Ag(111) substrate. Hydrogen bonds between pyridyl and pyrrole groups of neighboring molecules as well as weak van der Waals forces between the pentyl chains stabilize the superstructure. Deposition of cobalt atoms onto the close-packed structure at room temperature leads to the formation of a hexagonal porous network stabilized by metal-ligand bonding between the pyridyl ligands and the cobalt atoms. Thermal annealing of the Co-coordination network at temperatures >450 K results in the transformation of the hexagonal network into a second close-packed structure. Changes in the molecule-substrate interactions due to metalation of the porphyrin core with Co as well as intermolecular interactions can explain the observed structural transformations.

show abstract

Section: Introductionmentioning

confidence: 99%

From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

Studener

Müller

Marets

et al. 2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…In other terms, the network would be a single component system. 15,43 Dealing with chiral coordination networks, 13,14 four design principles may be explored: the combination of a chiral organic tecton and a metal centre, the combination of a chiral organic tecton and an achiral metal complex as a metallatecton, the combination of an achiral organic tecton with a chiral metal complex and finally, the combination of a chiral organic tecton with a chiral metallatecton.…”

Section: Design Of Ligandsmentioning

confidence: 99%

“…Furthermore, as previously demonstrated, the topology of the networks also strongly depends on the crystallization conditions such as temperature, concentration of the component, the nature and the ratio of the solvent/nonsolvent system used, the speed of diffusion/evaporation, etc. 43,58,60,66 Structural investigations of the chiral coordination network formed by (R,R)-1-Zn Single crystals (monoclinic C2, see Experimental section) of Zn-(R,R)-1 were obtained from a solution of (R,R)-1 and Zn(OAc) 2 in DMF (see Experimental section for crystallisation conditions). The X-ray diffraction analysis revealed the formation of a chiral 1D network formed upon self-assembly of the (R,R)-1-Zn selfcomplementary tecton (Fig.…”

Section: Chiral Coordination Networkmentioning

confidence: 99%

“…The possibility of incorporating both a metal centre within the tetraaza core of the porphyrin offering free coordination sites and peripheral groups displaying coordinating sites is another interesting feature since it allows us to design selfcomplementary metallatectons. Among many porphyrin based coordination networks reported to date, [38][39][40][41][42][43][44][45] only a few are based on chiral porphyrins. [46][47][48][49][50][51][52][53][54][55][56][57][58] We and others have explored the formation of coordination networks by Zn(porphyrin) based metallatectons bearing one, two or four pyridyl units at the meso position.…”

Section: Introductionmentioning

confidence: 99%

“…[46][47][48][49][50][51][52][53][54][55][56][57][58] We and others have explored the formation of coordination networks by Zn(porphyrin) based metallatectons bearing one, two or four pyridyl units at the meso position. 42,43,[59][60][61][62][63][64][65][66] Here, we report on the design, synthesis and characterisation of four new chiral porphyrin ligands ((S,S)-1, (R,R)-1 and (S,S)-2 (R,R)-2), and their use for the generation of 1-and 2-D chiral coordination networks in the presence of the Zn(II) cation ((S,S)-1-Zn, (R,R)-1-Zn and (S,S)-2-Zn, (R,R)-2-Zn).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Molecular tectonics: chiral 1- and 2-D zinc coordination networks based on chiral porphyrins bearing pyridyl and ethynylpyridyl appended units

2013

View full text Add to dashboard Cite

Synthesis and Solution Studies of Silver(I)‐Assembled Porphyrin Coordination Cages

Durot¹,

Flamigni²,

Taesch³

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

The synthesis and the characterization of two porphyrin coordination cages are reported. The design of the cage formation is based on the coordination of silver(I) ions to the pyridyl units of 3-pyridyl appended porphyrins. (1)H/(109)Ag NMR spectroscopy, and diffusion-ordered spectroscopy (DOSY) experiments demonstrate that both the free base porphyrin 2H-TPyP and the Zn-porphyrin Zn-TPyP form the closed cages, [Ag4(2H-TPyP)2](4+) and [Ag4(Zn-TPyP)2](4+), respectively, upon addition of two equivalents of Ag(+). The complexation processes are characterized in details by means of absorption and emission spectroscopy in diluted CH2Cl2 solutions. The data are discussed in the frame of the point-dipole exciton coupling theory; the two porphyrin monomers, in fact, experience a rigid face-to-face geometry in the cages and a weak inter-porphyrin exciton coupling. An intermediate species is observed, for Zn-TPyP, in a porphyrin/Ag(+) stoichiometric ratio of about 1:0.5 and is tentatively ascribed to an oblique open form. The occurrence of a photoinduced electron-transfer reaction within the cages is excluded on the basis of the experimental outcomes and thermodynamic evaluations. Photophysical experiments evidence different reactivities of singlet and triplet excited states in the assemblies. A lower fluorescence quantum yield and triplet formation is discussed in relation to the constrained geometry of the complexes. Unusually long triplet excited state lifetimes are measured for the assemblies.

show abstract

62 Porphyrin-Based Tectons in Molecular Tectonics

Cited by 7 publications

References 99 publications

From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

From hydrogen bonding to metal coordination and back: Porphyrin-based networks on Ag(111)

Molecular tectonics: chiral 1- and 2-D zinc coordination networks based on chiral porphyrins bearing pyridyl and ethynylpyridyl appended units

Synthesis and Solution Studies of Silver(I)‐Assembled Porphyrin Coordination Cages

Contact Info

Product

Resources

About