Numerical Simulations: All the numerical simulations were performed on SIMPSON. Frequencies are denoted as 𝜈 5 *6(7869 , where 𝛼 represent the interaction such as CSA, QC, RF, dipole etc. The Optimal Control (OC) simulations used a first order conjugate gradient method with tolerance levels for line search and target gradient being set to 10 -7 and 10 -8 , respectively. The virtual spectrometer operating at 1 H Larmor frequency, 𝜈 1 2 of 400 MHz and Magic Angle Spinning (MAS) frequency, 𝜈 -of 42 kHz (rotor period becomes 23.8 𝜇s) were used. A spin system consisting of three 19 F and one 7 Li spins was used to accommodate the effect of 19 F CSA, 19 F- 19 F dipolar coupling and 7 Li quadrupolar interaction along with the 19 F-7 Li dipolar coupling. RF amplitudes as an initial guess for OC were restricted to a maximum 𝜈 :$ $ = 90 kHz and 𝜈 :$ &' = 80 kHz for 19 F and 7 Li, respectively. Initial phase and amplitudes guesses were lists of 5000 random numbers for each within the restrictions. The total mixing time was 63 rotor periods (1.5 ms) such that each pulse length was 1.5ms/5000. The dipolar couplings of 19 F-19 F, 𝜈 4'; $<$ and 19 F-7 Li, 𝜈 4'; $<&' were set to 10 kHz and 6 kHz and first order QC, 𝜈 % &' of 7 Li was considered and was set to 250 kHz. The CSA of all 19 F nucleus 𝜈 !"# $ was set to 210 ppm (i.e. 79 kHz at 9.4 T) and the isotropic chemical shifts 𝜈 !"('>?) $ of all three 19 F was set to 0 ppm. The pictorial representation of simulation environment is depicted in Figure , Supplementary Information (SI). Initial state was defined by 𝐼 A operator of all three 19 F nucleus and final state was defined by Ip of 7 Li nucleus. Since the optimizations with 𝜈 !"# $ = 210 ppm didn't converse in after weeks of computational time, we used a two-step procedure to ensure the conversance. First, an optimal shape for 5000 points was obtained starting from a random guess with 𝜈 !"# $ = 50 ppm and remaining parameters same as mentioned above. Then this shape was used as initial guess to optimize the pulse for 𝜈 !"# $ = 210 ppm. This total optimization was done on 8 core AMD CPU with 19 days in total optimization time (5 days for the initial optimization and 14 days for re-optimization). For simulating the 19 F-7 Li polarization transfer curves and the performance of the pulse sequence under varying experimental and sample conditions, the optimal shapes were compressed to one rotor period and repeated during the mixing time (t ()*+,(+ ). The simulations to examine the efficiency were conducted at both 9.4 T, 42 kHz MAS and 14.1 T, 30 kHz MAS conditions to show the applicability of the present method and a proper comparison with the experimental data that were recorded at 600 MHz spectrometer (details below). Similarly, 19 F-27 Al, 19 F- 23 Na and 19 F-13 C polarization transfer curves were simulated with 𝜈 !"#