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Revealing the Real Size of a Porphyrin Molecule with Quantum Confinement Probing via Temperature-Dependent Photoluminescence Spectroscopy

Nurhayatia, Suendo V.a, Alni A.a, Nugroho A.A.a, Majima Y.b, Lee S.b, Nugraha Y.P.a, Uekusa H.b

a Division of Inorganic and Physical Chemistry, Faculty Mathematics and Natural Sciences, Institut Teknologi Bandung, Bandung, 40132, Indonesia
b Laboratory for Materials and Structures, Tokyo Institute of Technology, Yokohama, 226-8503, Japan

[vc_row][vc_column][vc_row_inner][vc_column_inner][vc_separator css=”.vc_custom_1624529070653{padding-top: 30px !important;padding-bottom: 30px !important;}”][/vc_column_inner][/vc_row_inner][vc_row_inner layout=”boxed”][vc_column_inner width=”3/4″ css=”.vc_custom_1624695412187{border-right-width: 1px !important;border-right-color: #dddddd !important;border-right-style: solid !important;border-radius: 1px !important;}”][vc_empty_space][megatron_heading title=”Abstract” size=”size-sm” text_align=”text-left”][vc_column_text]Copyright © 2020 American Chemical Society.The confinement energy of electrons in an aromatic molecule was studied by indirect and direct methods, namely, temperature-dependent photoluminescence (TDPL) spectroscopy and scanning tunneling microscopy (STM). We observed a decrease in the tetraphenylporphyrin (H2TPP) PL intensity with increasing temperature. The increase in temperature provides kinetic energy for the electrons to overcome the confinement energy barrier, making recombination via nonradiative pathways more favorable. The results of fitting the integrated TDPL intensity with a modified Arrhenius equation suggest two confinement energy values. We propose that these energy values are related to the size of the delocalized electron cloud along the plane and thickness of the H2TPP ring. These values quantitatively express an abstract form of the size of the aromatic ring system. These results are in good agreement with the topography images of single H2TPP molecules and monolayer H2TPP obtained by a direct probing method using STM. These results are also supported by the porphyrin ring orientation relative to the excited crystal face during the TDPL measurements.[/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”Author keywords” size=”size-sm” text_align=”text-left”][vc_column_text]Aromatic ring system,Delocalized electron,Increasing temperatures,Modified arrhenius equations,Porphyrin molecules,Temperature dependent photoluminescences,Temperature-dependent photoluminescence spectroscopies,Tetraphenyl porphyrins[/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”Indexed keywords” size=”size-sm” text_align=”text-left”][vc_column_text][/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”Funding details” size=”size-sm” text_align=”text-left”][vc_column_text]The authors acknowledge the financial support provided by CRP program 2017 and 2018 (Collaborative Research Projects of the Materials and Structures Laboratory, Tokyo Institute of Technology). V.S. acknowledges the Ministry of Research, Technology and Higher Education of the Republic of Indonesia for financial support through Penelitian Dasar Unggulan Perguruan Tinggi (PDUPT) Research Grant 2016, 2019, and 2020. N. acknowledges the Ministry of Finance, the Republic of Indonesia, for funding this research through the Indonesia Endowment Fund for Education (LPDP) Scholarship Program. Y.M. is grateful for the support of the MEXT Elements Strategy Initiative to Form Core Research Centers and BK Plus Program, the Basic Science Research Program (NRF-2014R1A6A1030419).[/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”DOI” size=”size-sm” text_align=”text-left”][vc_column_text]https://doi.org/10.1021/acs.jpca.0c00665[/vc_column_text][/vc_column_inner][vc_column_inner width=”1/4″][vc_column_text]Widget Plumx[/vc_column_text][/vc_column_inner][/vc_row_inner][/vc_column][/vc_row][vc_row][vc_column][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][/vc_column][/vc_row]