Photothermal　catalytic　N-acetylation　of　aniline　has　been　a　promising　strategy　to　synthesize　amides,　which　combined　the　advantages　of　thermal　catalysis　and　photocatalysis.　Herein,　we　demonstrate　a　high-performance　strategy　to　synthesize　amides　catalyzed　by　the　in-situ　formed　first-row　transition-metal　(Fe,　Co,　Ni,　Mn　et　al.)　complexes　nanodots　(TMC　NDs)　under　solar　light　excitation　without　using　noble　metals　or　strong　acids.　The　dual-functional　nitriles　substrates　acted　as　the　ligands　to　coordinate　with　transition-metal　salts　affording　photosensitive　TMC　NDs　with　high　solar-to-thermal　energy　conversion　efficiency.　Intramolecular　charge　transitions　reduced　the　energy　barrier　of　nitriles　activation　by　weakening　C[tbnd]N　bond　and　triggered　near-field　temperature　rise　via　the　electron–phonon　scattering　non-radiative　pathway.　The　reaction　system　exhibited　good　tolerance　to　different　functional　groups,　affording　a　series　of　amide　derivatives.　Such　a　dynamic　coordination　reaction　mode　and　the　in-situ　formed　TMC　NDs　opens　new　avenues　toward　solar-heat　conversion　via　photon–phonon　coupling　in　the　field　of　chemical　synthesis.　©　2023　Elsevier　B.V.