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　dualfunctional　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---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.