Using a data sample of e⁺e⁻ collision data corresponding to an integrated luminosity of 19 fb⁻¹ collected with the BESIII detector at the BEPCII collider, we search for the production of deuterons and antideuterons via e⁺e⁻→ ppπ⁻d̄+c.c. for the first time at center-of-mass energies between 4.13 and 4.70 GeV. No significant signal is observed and the upper limit of the e⁺e⁻→ ppπ⁻d̄+c.c. cross section is determined to be from 9.0 to 145 fb depending on the center-of-mass energy at the $90%$ confidence level.
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