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Durbeej, Bo, ProfessorORCID iD iconorcid.org/0000-0001-5847-1196
Publications (10 of 48) Show all publications
Arpa González, E. M., Stafström, S. & Durbeej, B. (2024). A Proof-of-Principle Design for Through-Space Transmission of Unidirectional Rotary Motion by Molecular Photogears. Chemistry - A European Journal, 30(2), Article ID e202303191.
Open this publication in new window or tab >>A Proof-of-Principle Design for Through-Space Transmission of Unidirectional Rotary Motion by Molecular Photogears
2024 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 30, no 2, article id e202303191Article in journal (Refereed) Published
Abstract [en]

The construction of molecular photogears that can achieve through-space transmission of the unidirectional double-bond rotary motion of light-driven molecular motors onto a remote single-bond axis is a formidable challenge in the field of artificial molecular machines. Here, we present a proof-of-principle design of such photogears that is based on the possibility of using stereogenic substituents to control both the relative stabilities of two helical forms of the photogear and the double-bond photoisomerization reaction that connects them. The potential of the design was verified by quantum-chemical modeling through which photogearing was found to be a favorable process compared to free-standing single-bond rotation ("slippage"). Overall, our study unveils a surprisingly simple approach to realizing unidirectional photogearing. A stereochemical approach to transmitting the directional double-bond rotary motion of light-driven molecular motors through space onto a remote single-bond axis is put forth and successfully tested by means of quantum-chemical modeling. A key result in the assessment of the approach is that the desired photogearing process is favorable compared to the undesired, free-standing single-bond rotation process ("slippage") with which it competes.**image

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2024
Keywords
density functional calculations; isomerization; molecular devices; molecular gears; photochemistry
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:liu:diva-199678 (URN)10.1002/chem.202303191 (DOI)001112531800001 ()37906675 (PubMedID)
Note

Funding Agencies|Vetenskapsrdet [2022-06725, 2018-05973]; Swedish Research Council [204-0183]; Olle Engkvist Foundation [CTS 20 : 102]; Carl Trygger Foundation

Available from: 2023-12-19 Created: 2023-12-19 Last updated: 2024-09-13Bibliographically approved
Arpa González, E. M., Stafström, S. & Durbeej, B. (2024). Photochemical formation of the elusive Dewar isomers of aromatic systems: why are substituted azaborines different?. Physical Chemistry, Chemical Physics - PCCP, 26(15), 11295-11305
Open this publication in new window or tab >>Photochemical formation of the elusive Dewar isomers of aromatic systems: why are substituted azaborines different?
2024 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 26, no 15, p. 11295-11305Article in journal (Refereed) Published
Abstract [en]

Photochemical reactions enabling efficient transformation of aromatic systems into energetic but stable non-aromatic isomers have a long history in organic chemistry. One recently discovered reaction in this realm is that where derivatives of 1,2-azaborine, a compound isoelectronic with benzene in which two adjacent C atoms are replaced by B and N atoms, form the non-hexagon Dewar isomer. Here, we report quantum-chemical calculations that explain both why 1,2-azaborine is intrinsically more reactive toward Dewar formation than benzene, and how suitable substitutions at the B and N atoms are able to increase the corresponding quantum yield. We find that Dewar formation from 1,2-azaborine is favored by a pronounced driving force that benzene lacks, and that a large improvement in quantum yield arises when the reaction of substituted 1,2-azaborines proceeds without involvement of an intermediary ground-state species. Overall, we report new insights into making photochemical use of the Dewar isomers of aromatic compounds. Quantum-chemical calculations combined with molecular-dynamics simulations reveal mechanisms for improving the quantum yields by which aromatic compounds form their non-aromatic Dewar isomers, with potential implications in solar-energy storage.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2024
National Category
Organic Chemistry
Identifiers
urn:nbn:se:liu:diva-202258 (URN)10.1039/d4cp00777h (DOI)001190620000001 ()38529645 (PubMedID)2-s2.0-85190717576 (Scopus ID)
Note

Funding Agencies|Vetenskapsrdet [2022-06725, 2018-05973]; Swedish Research Council [204-0183]; Olle Engkvist Foundation [CTS 20:102]; Carl Trygger Foundation

Available from: 2024-04-09 Created: 2024-04-09 Last updated: 2025-02-18Bibliographically approved
Thillaiarasi, T., Perumalla, D. S., Oruganti, B. & Durbeej, B. (2024). Polycyclic Heteroaromatic p-Linkers Provide Dithienylethene Switches with Favorable Thermal and Photochemical Properties for Solar-Energy Storage. ChemPhotoChem, 8(7), Article ID e202300225.
Open this publication in new window or tab >>Polycyclic Heteroaromatic p-Linkers Provide Dithienylethene Switches with Favorable Thermal and Photochemical Properties for Solar-Energy Storage
2024 (English)In: ChemPhotoChem, E-ISSN 2367-0932, Vol. 8, no 7, article id e202300225Article in journal (Refereed) Published
Abstract [en]

Dithienylethene photoswitches with an aromatic pi-linker as the bridge between the two thiophene units are attractive starting materials for developing molecular solar thermal energy (MOST) storage systems, partly because the aromaticity of their ring-open forms is a favorable feature with regard to the energy-storage densities of their ring-closed forms produced by photoinduced electrocyclization (photocyclization) reactions. At the same time, this typically leads to small barriers for their thermal cycloreversion reactions, which are not desirable in this context. Here, we use computational methods to show that this problem can be circumvented with polycyclic heteroaromatic pi-linkers. Specifically, through the tuning of the aromatic character of the individual rings of such a pi-linker (like indole or isoindole), it is shown to be possible to strike a delicate balance between the seemingly contrasting requirements of simultaneously achieving both a high energy-storage density and a large cycloreversion barrier. Furthermore, this design is also found to provide for a quick and efficient photocyclization reaction, owing to the onset of excited-state antiaromaticity in the pi-linker upon light absorption of the ring-open form. Altogether, dithienylethenes with polycyclic heteroaromatic pi-linkers appear to have both thermal and photochemical properties suitable for further development into future MOST systems. Through the incorporation of a polycyclic heteroaromatic pi-linker between their thiophene units, dithienylethene switches are shown computationally to exhibit a photocyclization reaction well exploitable for solar-energy storage, while also occupying a sweet spot for such applications where contrasting requirements on energy-storage densities and thermal cycloreversion barriers can be met. image

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2024
Keywords
aromaticity; energy conversion; heterocycles; molecular dynamics; molecular photoswitches
National Category
Energy Systems
Identifiers
urn:nbn:se:liu:diva-201841 (URN)10.1002/cptc.202300225 (DOI)001173802300001 ()2-s2.0-85186250425 (Scopus ID)
Note

Funding Agencies|Swedish Research Council; Olle Engkvist Foundation [204-0183]; Carl Trygger Foundation [CTS 20:102, CTS 21:1545]; Department of Science and Technology (DST), New Delhi, India [SUR/2022/001766]; SRM University-AP; National Academic Infrastructure for Supercomputing in Sweden - Swedish Research Council [2022-06725, 2018-05973]; [2019-03664]

Available from: 2024-03-25 Created: 2024-03-25 Last updated: 2025-03-04Bibliographically approved
Lv, J., Fang, C., Zhu, C., Sun, P., Li, Y. Y., Durbeej, B., . . . Deng, L. (2022). Numerical Investigation of the Stimulated Growth of Single-Crystal Fibers by Point-Effect-Induced Fluid Dynamics. Crystal Growth & Design, 22(12), 7031-7039
Open this publication in new window or tab >>Numerical Investigation of the Stimulated Growth of Single-Crystal Fibers by Point-Effect-Induced Fluid Dynamics
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2022 (English)In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 22, no 12, p. 7031-7039Article in journal (Refereed) Published
Abstract [en]

Using molecular dynamics analysis and a two-component diffusion model that accounts for the time-dependent crystal surface chemical reaction, we show by extensive numerical simulations that the recently observed prismatic facet growth suppression in single-crystal fibers is the combined action of self-shielding by crystal surface selectivity and self-channeling arising from a point effect due to fibers small diameters and large aspect ratios. We further show that the self-channeling leads to a pyramidal-face-aiming solute flow, resulting in accelerated single-crystal fiber growth. This mesoscopic stimulated matter growth acceleration theory can satisfactorily explain all experimental results reported to date. This new crystal fiber growth technology opens a realm of application possibilities for single-crystal fiber architectures in chip-size photonics.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2022
National Category
Physical Chemistry
Identifiers
urn:nbn:se:liu:diva-190213 (URN)10.1021/acs.cgd.2c00690 (DOI)000883665400001 ()
Note

Funding Agencies|Natural Science Foundation of Shandong Province; Fundamental Research Funds of Shandong University; National Natural Science Foundation of China; Primary Research & Development Plan of Shandong Province; [61975154]; [2017CXGC0413]

Available from: 2022-11-30 Created: 2022-11-30 Last updated: 2023-11-07Bibliographically approved
Wang, J. & Durbeej, B. (2022). Thermal Fluctuations in Conjugation and their Effect on Calculated Excitation Energies: A Case Study on the Astaxanthin Carotenoid. ChemPhotoChem, 6(1), Article ID e202100178.
Open this publication in new window or tab >>Thermal Fluctuations in Conjugation and their Effect on Calculated Excitation Energies: A Case Study on the Astaxanthin Carotenoid
2022 (English)In: ChemPhotoChem, E-ISSN 2367-0932, Vol. 6, no 1, article id e202100178Article in journal (Refereed) Published
Abstract [en]

A popular approach to the calculation of molecular excitation energies is to consider only equilibrium geometries and neglect the effects of thermal motion. Although this static approach is sensible for molecules with distinct potential-energy minima, its adequacy relative to dynamical approaches appears not to have been thoroughly tested. Here, we report a case study investigating how thermal motion accounted for by molecular dynamics simulations influences the optically bright state of astaxanthin, a carotenoid of broad photobiological interest that features 13 conjugated double bonds. Employing several different density functional methods, it is shown that thermal fluctuations in the conjugation result in the Boltzmann-weighted average excitation energies for this state being shifted by up to 0.05 eV relative to those obtained from purely static calculations. Accordingly, it is concluded that the effects of thermal motion on excitation energies of conjugated systems can be quite large even for molecules with distinct potential-energy minima.

Place, publisher, year, edition, pages
Weinheim, Germany: Wiley-VCH Verlagsgesellschaft, 2022
Keywords
Bond-length alternation, Carotenoids, Conjugation, Density functional calculations, Molecular dynamics
National Category
Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-180318 (URN)10.1002/cptc.202100178 (DOI)000710004500001 ()
Funder
Olle Engkvists stiftelse, 184-568 and 204-0183Swedish Research Council, 2019-03664ÅForsk (Ångpanneföreningen's Foundation for Research and Development), 20-570Carl Tryggers foundation , CTS 20:102
Note

Funding: Olle Engkvist Foundation [184-568, 204-0183]; Swedish Research CouncilSwedish Research CouncilEuropean Commission [2019-03664, 2018-05973]; AForsk [20-570]; Carl Trygger Foundation [CTS20:102]; Linkoping University

Available from: 2021-10-13 Created: 2021-10-13 Last updated: 2022-07-26
Arpa González, E. M. & Durbeej, B. (2022). Transient changes in aromaticity and their effect on excited-state proton transfer reactions. Physical Chemistry, Chemical Physics - PCCP, 24(19), 11496-11500
Open this publication in new window or tab >>Transient changes in aromaticity and their effect on excited-state proton transfer reactions
2022 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 24, no 19, p. 11496-11500Article in journal (Refereed) Published
Abstract [en]

The common approach to investigate the impact of aromaticity on excited-state proton transfer by probing the (anti)aromatic character of reactants and products alone is scrutinized by modelling such reactions involving 2-pyridone. Thereby, it is found that energy barriers can be strongly influenced by transient changes in aromaticity unaccounted for by this approach, particularly when the photoexcited state interacts with a second excited state. Overall, the modelling identifies a pronounced effect overlooked by most studies on this topic.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2022
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:liu:diva-185019 (URN)10.1039/d2cp00494a (DOI)000790479900001 ()35507952 (PubMedID)
Note

Funding Agencies|Olle Engkvist Foundation [204-0183]; Swedish Research Council [2019-03664, 2018-05973]; AForsk [20-570]; Carl Trygger Foundation [CTS 20 : 102]; Linkoping University

Available from: 2022-05-18 Created: 2022-05-18 Last updated: 2022-06-20
Durbeej, B. (2020). Competing Excited-State Deactivation Processes in Bacteriophytochromes. In: Kenneth Ruud, Erkki J. Brändas (Ed.), Chemical Physics and Quantum Chemistry: (pp. 243-268). Elsevier, 81
Open this publication in new window or tab >>Competing Excited-State Deactivation Processes in Bacteriophytochromes
2020 (English)In: Chemical Physics and Quantum Chemistry / [ed] Kenneth Ruud, Erkki J. Brändas, Elsevier, 2020, Vol. 81, p. 243-268Chapter in book (Refereed)
Abstract [en]

Bacteriophytochromes are photoreceptor proteins of widespread use as templates for the engineering of fluorescent proteins with emission maxima in the near-infrared regime beyond 650 nm ideally suited for deep-tissue imaging of living cells. The main challenge for such engineering is that native bacteriophytochromes have very low fluorescence quantum yields because of competing excited-state deactivation processes, which include both the well-known photoisomerization reaction of their linear tetrapyrrole chromophore and excited-state proton transfer reactions from the chromophore to the surrounding protein. Here, we describe how hybrid quantum mechanics/molecular mechanics modeling of the photochemistry of these proteins has provided valuable guidelines for strengthening the fluorescence through inhibition of the competing non-radiative processes. Specifically, based on the results of such modeling, we present a strategy to inhibit the photoisomerization on steric grounds and identify the most probable proton transfer reaction to exert a negative influence on the fluorescence quantum yields. It is our hope that these results will help stimulate further contributions from quantum chemistry toward realizing the potential for entirely new bioimaging applications commonly attributed to brightly near-infrared fluorescent bacteriophytochromes.

Place, publisher, year, edition, pages
Elsevier, 2020
Series
Advances in Quantum Chemistry, ISSN 0065-3276
Keywords
Near-infrared fluorescent proteins, Photoreceptor proteins, Tetrapyrrole chromophores, Quantum yields, Photoisomerization, Excited-state proton transfer, Photoacids, QM/MM modeling, Time-dependent density functional theory, Range-separated functionals
National Category
Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-166050 (URN)10.1016/bs.aiq.2020.05.003 (DOI)000608840200009 ()2-s2.0-85085758238 (Scopus ID)9780128197578 (ISBN)
Funder
Swedish Research Council, 621-2011-4353 and 2019-03664Olle Engkvists stiftelse, 2014/734 and 184-568
Note

Funding agencies:Swedish Research CouncilSwedish Research Council [621-2011-4353, 2019-03664]; Olle Engkvist Foundation [2014/734, 184-568]; National Supercomputer Centre (NSC) at Linkoping University

Available from: 2020-06-06 Created: 2020-06-06 Last updated: 2022-09-01Bibliographically approved
Wang, J. & Durbeej, B. (2020). How accurate are TD-DFT excited-state geometries compared to DFT ground-state geometries?. Journal of Computational Chemistry, 41(18), 1718-1729
Open this publication in new window or tab >>How accurate are TD-DFT excited-state geometries compared to DFT ground-state geometries?
2020 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 41, no 18, p. 1718-1729Article in journal (Refereed) Published
Abstract [en]

In this work, we take a different angle to the benchmarking of time-dependent density functional theory (TD-DFT) for the calculation of excited-state geometries by extensively assessing how accurate such geometries are compared to ground-state geometries calculated with ordinary DFT. To this end, we consider 20 medium-sized aromatic organic compounds whose lowest singlet excited states are ideally suited for TD-DFT modeling and are very well described by the approximate coupled-cluster singles and doubles (CC2) method, and then use this method and six different density functionals (BP86, B3LYP, PBE0, M06-2X, CAM-B3LYP, and omega B97XD) to optimize the corresponding ground- and excited-state geometries. The results show that although each hybrid functional reproduces the CC2 excited-state bond lengths very satisfactorily, achieving an overall root mean square error of 0.011 angstrom for all 336 bonds in the 20 molecules, these errors are distinctly larger than those of only 0.004-0.006 angstrom with which the hybrid functionals reproduce the CC2 ground-state bond lengths. Furthermore, for each functional employed, the variation in the error relative to CC2 between different molecules is found to be much larger (by at least a factor of 3) for the excited-state geometries than for the ground-state geometries, despite the fact that the molecules/states under investigation have rather uniform chemical and spectroscopic character. Overall, the study finds that even in favorable circumstances, TD-DFT excited-state geometries appear intrinsically and comparatively less accurate than DFT ground-state ones.

Place, publisher, year, edition, pages
WILEY, 2020
Keywords
ab initio methods; aromatic organic compounds; benchmark; density functional theory; excited-state geometries
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:liu:diva-165568 (URN)10.1002/jcc.26213 (DOI)000527796000001 ()32323870 (PubMedID)
Note

Funding Agencies|Linkopings Universitet; Stiftelsen Olle Engkvist ByggmastareSwedish Research Council [184-568]; VetenskapsradetSwedish Research Council [2019-03664]

Available from: 2020-05-06 Created: 2020-05-06 Last updated: 2022-06-20
Oruganti, B., Kalapos, P. P., Bhargav, V., London, G. & Durbeej, B. (2020). Photoinduced Changes in Aromaticity Facilitate Electrocyclization of Dithienylbenzene Switches. Journal of the American Chemical Society, 142(32), 13941-13953
Open this publication in new window or tab >>Photoinduced Changes in Aromaticity Facilitate Electrocyclization of Dithienylbenzene Switches
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2020 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 142, no 32, p. 13941-13953Article in journal (Refereed) Published
Abstract [en]

The concepts of excited-state aromaticity and antiaromaticity have in recent years with increasing frequency been invoked to rationalize the photochemistry of cyclic conjugated organic compounds, with the long-term goal of using these concepts to improve the reactivities of such compounds toward different photochemical transformations. In this regard, it is of particular interest to assess how the presence of a benzene motif affects photochemical reactivity, as benzene is well-known to completely change its aromatic character in its lowest excited states. Here, we investigate how a benzene motif influences the photoinduced electrocyclization of dithienylethenes, a major class of molecular switches. Specifically, we report on the synthesis of a dithienylbenzene switch where the typical nonaromatic, ethene-like motif bridging the two thienyl units is replaced by a benzene motif, and show that this compound undergoes electrocyclization upon irradiation with UV-light. Furthermore, through a detailed quantum chemical analysis, we demonstrate that the electrocyclization is driven jointly and synergistically by the loss of aromaticity in this motif from the formation of a reactive, antiaromatic excited state during the initial photoexcitation, and by the subsequent relief of this antiaromaticity as the reaction progresses from the Franck-Condon region. Overall, we conclude that photoinduced changes in aromaticity facilitate the electrocyclization of dithienylbenzene switches. 

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020
Keywords
Aromatic compounds, Photocyclization, Excited states, Molecular switches, Quantum chemical calculations, Molecular dynamics simulations, Organic synthesis
National Category
Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-167809 (URN)10.1021/jacs.0c06327 (DOI)000562942200035 ()
Funder
Stiftelsen Olle Engkvist Byggmästare, 184-568 and 204-0183Swedish Research Council, 2019-03664
Note

Funding agenceis:  Olle Engkvist Foundation [184-568, 204-0183]; Swedish Research CouncilSwedish Research Council [2019-03664]; Hungarian Academy of Sciences through the Lendulet Program [LENDULET_2018_355]; National Research, Development and Innovation Office, Hungary (NKF

Available from: 2020-07-29 Created: 2020-07-29 Last updated: 2020-09-12
Wang, J., Oruganti, B. & Durbeej, B. (2020). Unidirectional Rotary Motion in Isotopically Chiral Molecular Motors: A Computational Analysis. Organic Letters, 22(18), 7113-7117
Open this publication in new window or tab >>Unidirectional Rotary Motion in Isotopically Chiral Molecular Motors: A Computational Analysis
2020 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 22, no 18, p. 7113-7117Article in journal (Refereed) Published
Abstract [en]

Molecular dynamics simulations are performed to explore if isotopic chirality can induce unidirectional rotary motion in molecular motors operated through double-bond photoisomerizations. Using a high-quantum yield motor featuring a chemically asymmetric carbon atom as reference, it is found that isotopically chiral counterparts of this motor sustain such motion almost equally well. Overall, the study reveals a previously unexplored role for isotopic chirality in the design of rotary molecular motors.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020
Keywords
Chirality, Isotope effects, Molecular motors, Photoisomerization, Aromaticity, Molecular dynamics simulations, Quantum chemical calculations
National Category
Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-168475 (URN)10.1021/acs.orglett.0c02436 (DOI)000574921100013 ()32822192 (PubMedID)
Funder
Swedish Research Council, 2019-03664Olle Engkvists stiftelse, 184-568 and 204-0183
Note

Funding Agencies|Olle Engkvist Foundation [184-568, 204-0183]; Swedish Research CouncilSwedish Research Council [2019-03664]

Available from: 2020-08-24 Created: 2020-08-24 Last updated: 2022-01-18Bibliographically approved
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ORCID iD: ORCID iD iconorcid.org/0000-0001-5847-1196

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