5 research outputs found
Triplet formation inhibits amplified spontaneous emission in perylene-based polycyclic aromatic hydrocarbons
Polycyclic Aromatic Hydrocarbons (PAHs) have demonstrated potential as active laser materials, showing good Amplified Stimulated Emission (ASE) properties. However, the molecular origin of their ASE properties is still unclear and depends on the particular compound. In this work we study the ASE properties of polystyrene films hosting three different perylene-based PAHs YZ-1, YZ-2 and YZ-3, where only YZ-3 has displayed ASE. Their molecular structure has been systematically changed to establish the connection between their molecular structure and their ASE properties. A complete spectroscopic study, with ground state and time-resolved techniques, show that, even at low yields, triplets play a critical role as a major loss mechanism. Their slow relaxation to ground state completely hinders the required unbalance of the S1 and S0 states for succesful ASE. Quantum chemical calculations suggest that a lower triplet density of states for YZ-3 is responsible for the blockage in triplet formation and, therefore, does not restrict ASE. This work not only presents a new PAH showing ASE, but also unequivocable proves the massive importance of triplet states in the development of organic lasers.JW acknowledges financial support from A*STAR AME grant (A20E5c0089). The group at the University of Alicante thanks financial support from the “Ministerio de Ciencia e InnovaciĂłn” (MCIN) of Spain and the European Regional Development Fund (grant No. PID2020-119124RB-I00) and from the Generalitat Valenciana though grant No. AICO/2021/093. Besides, this study is part of the Advanced Materials program supported by the Spanish MCIN with funding from European Union Next Generation EU and by Generalitat Valenciana (grant no. MFA/2022/045). The group at the UA thanks Dr. J.M Villalvilla and Dr. J.A. Quintana for useful discussions. We also thank the Research Central Services (SCAI) of the University of Málaga for the access to the EVI, EEL and MENL to perform ground state and transient spectroscopic characterisation. JC thanks funding provided by MINECO/FEDER (PID2021-127127NB-I00, PID2019-110305GB-I00) and Junta de AndalucĂa (PROYEXCEL-0328)
Medium Diradical Character, Small Hole and Electron Reorganization Energies and Ambipolar Transistors in Difluorenoheteroles
Four difluorenoheteroleshavinga centralquinoidalcore with the heteroringvaryingas furan,thiophene,its dioxidederivativeand pyrrolehave shownto be mediumcharacterdiradicals.Solid-statestructures,optical,photophysical,magnetic,and electrochemicalpropertieshave been discussedin termsof diradicalcharacter,variationof aromaticcharacterand captoda-tive effects(electronaffinity).Organicfield-effecttran-sistors(OFETs)have been prepared,showingbalancedholeand electronmobilitiesof the orderof103cm2V1s1or ambipolarchargetransportwhichisfirst inferredfrom their redoxamphoterism.Quantumchemicalcalculationsshow that the electricalbehaviorisoriginatedfrom the mediumdiradicalcharacterwhichproducessimilarreorganizationenergiesfor hole andelectrontransports.The visionof a diradicalas simulta-neouslybearingpseudo-holeand pseudo-electronde-fects might justifythe reducedvaluesof reorganizationenergiesfor both regimes.Structure-functionrelation-ships betweendiradicaland ambipolarelectricalbehav-ior are revealed.The authorsthankthe SpanishMinistryof ScienceandInnovation(projectsMINECO/FEDERPGC2018-098533-B-100,and PID2019-110305GB-I00),the Junta de AndalucĂaand GeneralidadValenciana,Spain (UMA18FEDERJA057,P18-FR-4549and Prometeo/2019/076)and JSPS KAKENHIgrant (JP21K05042for S.-i.K.,JP21K04995and JP21H05489for R.K., JP21H01887and JP20K21173for M.N.).S.-i.K.gratefullyacknowledgesthe AsahiGlassFoundationforfinancialsupport.We also thankthe ResearchCentralServices(SCAI)of the Universityof Málaga,UnidaddeEspectroscopĂaVibracional(Dra. Capely Dr. Zafra)andUnidadde OpticaNo-Linealy EspectroscopĂaUltrarápida(Dr. Román).This work was partiallysupportedby theCooperativeResearchProgram“NetworkJoint ResearchCenterfor Materialsand Devices”(KyushuUniversity).WethankProf. ShuheiHigashibayashi(KeioUniversity)forassistancewith synthesis.Mass spectrometricdata werecollectedat HiroshimaUniversity(N-BARD:Ms. TomokoAmimoto).Theoreticalcalculationswere partlyperformedusing ResearchCenterfor ComputationalScience(R-CCS),Okazaki,Japan.F.N and Y.D. acknowledgesupportfrom“Valutazionedella Ricercadi Ateneo”(VRA)—Universityof Bologna.Y.D. acknowledgesMinisterodell’UniversitĂ edella Ricerca(MUR)for her Ph.D. fellowship.
Funding for open access charge: Universidad de Málaga / CBU
The heteroatom effect in ambipolar diradicals.
Contribución tipo Póster con Flash oralThe ability to efficiently transport both holes and electrons makes ambipolar organic materials appealing architectures in organic electronics for the development of p- and n-channel devices. However, most of the organic semiconductors do not exhibit ambipolar behaviour mainly due to their intrinsic electronic properties (energetic mismatch between their frontier molecular orbitals and the Fermi levels of the metals used as drain and source electrodes) and to charge trapping at OFET–gate dielectric interfaces. The search of new ambipolar materials is closely related to the examination of the redox amphoterism in π-conjugated structures, i.e., the capacity to equally accommodate positive and negative charges. In this context, the small HOMO-LUMO gap of π-conjugated molecules showing an incipient or medium diradical character makes them good candidates to display p–n balanced mobilities. Several open-shell molecules, such as a diindeno[b,i]anthracene derivative, zethrenes and diindenoperylenes, have been reported as efficient ambipolar materials indeed.
In this communication we present a series of four difluorenoheteroles (DFX) with identical chemical structure except for the role of the heteroatom which is played by Oxygen, Nitrogen, Sulphur and Sulphur dioxide. The entire DFX series exhibit a medium diradical character as consequence of the combination of electronic affinity, captodative effect and aromatic stabilization. Addressing the electronic properties of the neutral, reduced and oxidized species of the DFX family we demonstrate their ambipolar electrical behaviour and elucidate the connection between their diradical character and the balance between the electron and hole transport.Universidad de Málaga. Campus de Excelencia Internacional AndalucĂa Tech
Oral delivery of oleuropein-loaded lipid nanocarriers alleviates inflammation and oxidative stress in acute colitis
V-Shaped Tröger Oligothiophenes Boost Triplet Formation by CT Mediation and Symmetry Breaking
A new family of molecules obtained by coupling Tröger’s base unit with dicyanovinylene-terminated oligothiophenes of different lengths has been synthesized and characterized by steady-state stationary and transient time-resolved spectroscopies. Quantum chemical calculations allow us to interpret and recognize the properties of the stationary excited states as well as the time-dependent mechanisms of singlet-to-triplet coupling. The presence of the diazocine unit in Tröger’s base derivatives is key to efficiently producing singlet-to-triplet intersystem crossing mediated by the role of the nitrogen atoms and of the almost orthogonal disposition of the two thiophene arms. Spin–orbit coupling-mediated interstate intersystem crossing (ISC) is activated by a symmetry-breaking process in the first singlet excited state with partial charge transfer character. This mechanism is a characteristic of these molecular triads since the independent dicyanovinylene-oligothiophene branches do not display appreciable ISC. These results show how Tröger’s base coupling of organic chromophores can be used to improve the ISC efficiency and tune their photophysics