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Compared with organic cations with flexible alkyl chains or rings, the HMHs with rigid aryl rings as the organic cations are more conducive to charge transfer and glass formation. However, their\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    values are generally high and the difference between the\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    and decomposition temperature is small, which is unfavorable for melting processing. Here, an\n                    <jats:italic>N<\/jats:italic>\n                    \u2010methylation design strategy of the phenylammonium cation is reported to lower the\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    and increase the fusible processing window to address these challenges. Three 2D HMHs (4\u2010F\/Cl\/Br\u2010NMA)\n                    <jats:sub>2<\/jats:sub>\n                    PbI\n                    <jats:sub>4<\/jats:sub>\n                    (\n                    <jats:bold>4F<\/jats:bold>\n                    \/\n                    <jats:bold>4Cl<\/jats:bold>\n                    \/\n                    <jats:bold>4Br<\/jats:bold>\n                    ; 4\u2010F\/Cl\/Br\u2010NMA = 4\u2010fluoro\/chloro\/bromo\u2010\n                    <jats:italic>N<\/jats:italic>\n                    \u2010methylaniline cation) are synthesized with aromatic amines as the A\u2010site cations, and their\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    values reach as low as 138\u00a0\u00b0C. Among them,\n                    <jats:bold>4F<\/jats:bold>\n                    has a large fusible processing window of 65\u00a0\u00b0C and a good glass conversion performance with a glass transition temperature to\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    ratio of 0.69. The mechanism to achieve the lowered\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    is ascribed to the methyl substitution on the nitrogen atom weakens the residual movement of the \u2500NH\n                    <jats:sub>2<\/jats:sub>\n                    \u2500 group through the conjugated delocalization effect between the benzene ring and the amino group, and thus reduces the hydrogen bonding interactions between the cations and inorganic layers. At the same time, the substitution of fluorine atoms on the benzene ring also helps to lower the\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    .\n                  <\/jats:p>","DOI":"10.1002\/smll.202507262","type":"journal-article","created":{"date-parts":[[2025,8,28]],"date-time":"2025-08-28T04:46:51Z","timestamp":1756356411000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["<i>N<\/i>\n                    \u2010Methylation and Fluorination of the Arylammonium Cation Enable Melting Point Suppression in Layered Hybrid Metal Halides"],"prefix":"10.1002","volume":"21","author":[{"given":"Rui","family":"Zuo","sequence":"first","affiliation":[{"name":"Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics and School of Chemistry and Chemical Engineering Southeast University  Nanjing 211189 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