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$\text{Hint: Isostructural species have the same hybridization and shape.}$ $\text{Step 1:}$ $\text{Isostructural species are those which have the same shape and hybridization.}$ $\text{Step 2:}$ $1.\ \text{PCl}_4^+\ \text{and}\ \text{SiCl}_4$ $\text{The hybridization of P in}\ \text{PCl}_4^+\ \text{and S in}\ \text{SiCl}_4\ \text{is}\ sp^3.\ \text{The shape of both compounds is tetrahedral. Thus, they are isostructural species.}$ $2.\ \text{PF}_5\ \text{and}\ \text{BrF}_5$ $\text{The hybridization of P in}\ \text{PF}_5\ \text{is}\ sp^3d\ \text{and the hybridization of Br in}\ \text{BrF}_5\ \text{is}\ sp^3d^2.\ \text{Hence, they are not an example of isostructural species.}$ $3.\ \text{AlF}_6^{3-}\ \text{and}\ \text{SF}_6$ $\text{The hybridization of Al in}\ \text{AlF}_6^{3-}\ \text{is}\ sp^3d^2\ \text{and S in}\ \text{SF}_6\ \text{is}\ sp^3d^2.\ \text{The shape of both species is the same that is octahedral. Hence, isostructural to each other.}$ $4.\ \text{CO}_3^{2-}\ \text{and}\ \text{NO}_3^-$ $\text{The hybridization of C in}\ \text{CO}_3^{2-}\ \text{is}\ sp^2\ \text{and N in}\ \text{NO}_3^-\ \text{is}\ sp^2.\ \text{The shape of both species is the same that is trigonal planar. Hence, isostructural to each other.}$ $\text{The correct answer is option second.}$