Comprehensive structure–function correlation of photoactive ionic π-conjugated supermolecular assemblies: an experimental and computational study

Adinehnia, Morteza; Borders, Bryan; Ruf, Michael; Chilukuri, Bhaskar; Hipps, K. W.; Mazur, Ursula

doi:10.1039/c6tc03957j

Cited by 32 publications

(83 citation statements)

References 91 publications

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“…2E). After 150-min solvent annealing, these aggregates transitioned into uniform square crystals with lateral dimensions of 200 to 500 nm and identifiable crystal faces, indicative of the emergent monoclinic crystal habit (34), as seen in Fig. 2F.…”

Section: Resultsmentioning

confidence: 93%

Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals

Muller

Gray

Zhou

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

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Much of the electronic transport, photophysical, or biological functions of molecular materials emerge from intermolecular interactions and associated nanoscale structure and morphology. However, competing phases, defects, and disorder give rise to confinement and many-body localization of the associated wavefunction, disturbing the performance of the material. Here, we employ vibrational excitons as a sensitive local probe of intermolecular coupling in hyperspectral infrared scattering scanning near-field optical microscopy (IR s-SNOM) with complementary small-angle X-ray scattering to map multiscale structure from molecular coupling to long-range order. In the model organic electronic material octaethyl porphyrin ruthenium(II) carbonyl (RuOEP), we observe the evolution of competing ordered and disordered phases, in nucleation, growth, and ripening of porphyrin nanocrystals. From measurement of vibrational exciton delocalization, we identify coexistence of ordered and disordered phases in RuOEP that extend down to the molecular scale. Even when reaching a high degree of macroscopic crystallinity, identify significant local disorder with correlation lengths of only a few nanometers. This minimally invasive approach of vibrational exciton nanospectroscopy and -imaging is generally applicable to provide the molecular-level insight into photoresponse and energy transport in organic photovoltaics, electronics, or proteins. infrared spectroscopy | molecular vibrations | scattering-scanning near-field optical microscopy (s-SNOM) | vibrational exciton | molecular energy transport

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Section: Resultsmentioning

confidence: 93%

Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals

Muller

Gray

Zhou

et al. 2020

Proc. Natl. Acad. Sci. U.S.A.

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“…For single crystal XRD evaluation, a Bruker D8 VENTURE single crystal diffractometer equipped with a Ga METALJET X-ray source (1.341398 Å) and Photon 100 detector was used for data acquisition from single crystal BP samples. The details of data collection and structural refinement for the free-base and metallated crystals are presented elsewhere [28][29][30].…”

Section: Materials and Sample Preparationmentioning

confidence: 99%

“…Each crystal was examined by XPS (x-ray photoelectron spectroscopy) to verify its stoichiometry and the actual protonation of the porphyrin tectons; spectra and analysis were published earlier [18,20,28,29,[34][35][36]. We note that heating the BP solids up to 130 °C did not modify their elemental charges or composition, based on X-ray photoelectron spectroscopy, (XPS) measurements [18,20,28,29,36]. Thermogravimetric analysis (TGA) combined with XPS showed that the crystals experienced reversible loss of water from within their crystalline channels at temperatures below 110 °C and became amorphous with annealing above 125 °C [29,30].…”

Section: Composition and Morphologymentioning

confidence: 99%

“…Here, we present a quantitative elastic properties and structure correlation study of a series of ionically self-assembled (ISA) [17][18][19][20] crystalline p-conjugated solids fabricated from oppositely charged porphyrin tectons (binary porphyrins, BP). These materials are known to serve as active components in many optoelectronic devices such as solar cells [21][22][23][24], photovoltaics [1,17,25], and photosensors [26][27][28][29][30]. Until recently, reports of crystal structures of BPs were rare because synthesized crystals were not suitable for single crystal X-ray diffraction (XRD) [31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

“…Until recently, reports of crystal structures of BPs were rare because synthesized crystals were not suitable for single crystal X-ray diffraction (XRD) [31][32][33][34]. However, by employing a newly developed crystal growth algorithm by Adinehnia and coworkers, it is now possible to efficiently produce nano-to millimetersized BP crystals in a controlled and reproducible manner [28,29,33,34]. Thus, this report is the first to relate the elastic modulus of single crystal ionic BPs to their molecular organization within the lattice of these anisotropic crystals.…”

Section: Introductionmentioning

confidence: 99%

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Mechanical behavior of crystalline ionic porphyrins

Adinehnia

Eskelsen

Hipps

et al. 2019

J. Porphyrins Phthalocyanines

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Mechanical properties of six different binary ionic porphyrin crystals with variable morphologies were measured and correlated with their structural properties. These solids were formed from stoichiometric combinations of negatively charged tectons, meso-tetra(4-sulfonatophenyl)porphyrin (TSPP), Cu(II) meso-tetra(4-sulfonatophenyl)porphyrin (CuTSPP), Ni(II) meso-tetra (4-sulfonatophenyl)porphyrin (NiTSPP), and four different cationic tectons, namely, meso-tetra (4-pyridyl)porphyrin (TPyP), tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (TMPyP), Cu(II) meso-tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (CuTMPyP), Ni(II) meso-tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (NiTMPyP), and tetra(4-aminophenyl)porphyrin (TAPP). Crystal structures were determined from single crystal and powder X-ray diffraction patterns. Scanning electron and atomic force microscopes (SEM and AFM) provided topographical information. The common arrangement of the porphyrin tectons within the crystals is consistent with alternating face-to-face molecular arrangement forming coherent columns along the fast-growing long axis which are held together by electrostatic and [Formula: see text]–[Formula: see text] interactions as well as hydrogen bonding. In acquiring the indentation data of the porphyrin crystals using AFM, stress was applied perpendicular to the direction where ionic and [Formula: see text]–[Formula: see text] bonds dominate the packing. At indent loads [Formula: see text]50 nN/nm2, all the porphyrin structures deformed elastically. Young’s modulus ([Formula: see text] values for the different crystals range from 6 to 28 GPa. In a broader perspective, this study highlights the extraordinary mechanical behavior of porphyrin assemblies formed by ionic self-assembly. Judicious selection of charged porphyrin synthons can yield crystalline materials with mechanical properties that combine the elastic characteristics of ‘soft’ polymers with the stiffness of composite materials. Such high-performance materials are excellent candidates for deformable optoelectronic devices.

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Phenothiazine‐Based Oligo(p‐phenylenevinylene)s: Substituents Affected Self‐Assembly, Optical Properties, and Morphology‐Induced Transport

Arivazhagan

Satapathy

Jana

et al. 2018

Chemistry A European J

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Designing intramolecular charge-transfer (ICT)-based luminogenic ordered assemblies exhibiting significant electrical transport is a challenging task in the field of organic optoelectronics. In this context, a series of novel phenothiazine-based oligo(p-phenylenevinylene) (OPV1-6) derivatives were designed and their structure-property relationship was investigated. Upon examining their photophysical properties, all the OPVs were found to exhibit significant intramolecular charge-transfer characteristics in organic solvents. While inspecting the self-assembly behaviour, the OPV with a long alkyl chain on the central phenyl core (OPV4) underwent gelation in organic solvent mixtures through strong hydrophobic interactions of the long hexadecyl chains and π-interactions from their aromatic counterparts. Computational studies revealed a lamellar packing of molecules in the assembly. Interestingly, the degree of ICT and the gelation abilities of OPVs were significantly influenced by the electronic nature of the substituents appended to the peripheral phenothiazines. Further, the AC impedance results revealed an increase in storage and electronic transport for the fluorescent thin films prepared by an increase in the content of OPV4 in PMMA.

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Comprehensive structure–function correlation of photoactive ionic π-conjugated supermolecular assemblies: an experimental and computational study

Abstract: Experimental and computational structure–function study of an organic crystalline photoconductor composed of oppositely charged ionic porphyrins.

Cited by 32 publications

References 91 publications

Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals

Vibrational exciton nanoimaging of phases and domains in porphyrin nanocrystals

Mechanical behavior of crystalline ionic porphyrins

Phenothiazine‐Based Oligo(p‐phenylenevinylene)s: Substituents Affected Self‐Assembly, Optical Properties, and Morphology‐Induced Transport

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