Partial answer, mostly a too long comment.
The basis of $\mathfrak g$ is the set [of] "generators" $\{t_\alpha\}$:
Any real Lie algebra $\mathfrak g \neq 0$ has infinitely many choices of bases, although some might be handier for computational purposes than others. Often people fix a basis somewhere early in the theory and then never bring up the issue if anything depends on that choice (some things don't, some do).
and the elements of G are obtained from the exponentiation of real linear combinations of $\{t_\alpha \}$.
What you are claiming here seems to be that the exponential map $exp: \mathfrak g \rightarrow G$ is surjective. In the general case, deciding whether this is true is a notoriously difficult question, cf. for example the answer https://math.stackexchange.com/a/3859991/96384 with further links, as well as On surjectivity of exponential map for Lie groups and https://mathoverflow.net/q/41644/27465 and https://en.wikipedia.org/wiki/Exponential_map_(Lie_theory)#Surjectivity_of_the_exponential.
To be fair, you restrict to the case that the Lie group $G$ is connected and simply connected. It is certainly true according to the above that then $G$ is generated by the image of the exponential, i.e. you can write any element of $G$ as a a product of exponentials of real linear combinations of your basis $\{t_\alpha\}$. Whether $exp$ is surjective, i.e. you can actually write each element as such an exponential (as opposed to a product of exponentials), I am not sure right now, but I doubt it. The standard example for non-surjectivity of $exp$ is the Lie group $SL_2(\mathbb R)$; now, that one is not simply-connected; what I guess is that if the exponential to its universal cover were surjective, then so would this one be; I am just not sure if this slick argument overlooks something.
What it does point out though is that the Lie-theoretic "exponential map" might be not just the matrix exponential, for which the above is an example: The matrix exponential of $\mathfrak{sl}_2(\mathbb R)$ lands in $SL_2(\mathbb R)$, but not in its universal cover (which is the simply connected Lie group you are looking for), which is "much bigger".
In this language, is the complexification of the vector space spanned by $\{t_\alpha\}$ a complex Lie algebra $\mathfrak g_{\mathbb C}$
Yes. The formal mathematical definition is with a tensor product, $\mathfrak g_{\mathbb C} := \mathbb C \otimes_{\mathbb R} \mathfrak g$. If $\{t_\alpha\}$ is a basis of $\mathfrak g$ (as a real vector space), then one can think of $\mathfrak g_{\mathbb C}$ as a complex vector space with "the same" basis, just that now complex linear combinations are allowed (formally, $\{1 \otimes t_\alpha\}$ is a basis of the complex space $\mathfrak g_\mathbb C$). Often it is useful to use different bases though.
and is the corresponding Lie group (where we instead use complex linear combinations of $\{t_\alpha\}$) a complex Lie group $G_{\mathbb C}$?
Too many things asked at once. There is a notion of complexification of Lie Groups, taking a real Lie group $G$ to a complex Lie group $G_\mathbb C$, which of course is made to commute in some way, via the Lie algebra - Lie group correspondence, with the complexification of Lie algebras. What you are asking might be,
if the complexification of the connected simply connected (real) Lie group corresponding to a real Lie algebra $\mathfrak g$, is the conneted simply connected (complex) Lie group corresponding to the complexified Lie algebra $\mathfrak g_\mathbb C$.
To be honest, again I am not sure. However, I am relatively sure that in the case $\mathfrak g = \mathfrak{sl}_2(\mathbb R)$, on the one hand, the simply connected connected complex Lie group corresponding to $\mathfrak g_\mathbb C = \mathfrak{sl}_2(\mathbb C)$ is just $SL_2(\mathbb C)$, whereas on the other hand, as said before, the simply connected connected real $G$ is huge (it is not a matrix gorup), and I very much doubt that its Lie-theoretic complexification would be $SL_2(\mathbb C)$.